Amino Acid, Carbohydrate and Acrylamide Polymers useful as Flocculants in Agricultural and Industrial Settings

ABSTRACT

Modified polysaccharides, acrylamide copolymers, water-soluble amino acid copolymers, and combinations thereof are described for uses including flocculation of solids, particularly flocculation of soil in an agricultural settings and clarification of process waters from oil-sands mining operations. Also described are methods of preparing selected amino acid copolymers and modified polysaccharides.

REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.12/090,216 filed Oct. 12, 2006, which issued as U.S. Pat. No. 9,994,767on Jun. 12, 2018, and is a National Stage Application of InternationalApplication No. PCT/US2006/40168 filed Oct. 12, 2006, and is acontinuation-in-part U.S. application Ser. No. 11/473,004 filed Jun. 22,2006, which issued as U.S. Pat. No. 7,595,002 on Sep. 29, 2009, and is acontinuation-in-part of U.S. application Ser. No. 11/472,958 filed Jun.22, 2006, which issued as U.S. Pat. No. 7,595,007 Sep. 29, 2009, andclaims priority to U.S. Provisional Application No. 60/726,721 filedOct. 14, 2005, each of which is specifically incorporated by reference.

FIELD OF THE INVENTION

The present invention relates to copolymers, modified polymers, andcombinations thereof having good water solubility and flocculationactivity. In particular, the invention relates to amino acid copolymers,polysaccharides, and acrylamide polymers having such properties, usedeither alone or in combination.

BACKGROUND

Copolymers of acrylic acid and acrylamide (PAM) were introduced forimprovement of soil quality via aggregation of soil particles over 50years ago (U.S. Pat. Nos. 2,625,529 and 2,652,380 to Hedrick and Mowry(1953) and U.S. Pat. No. 2,652,381 to Basdekis (1953)). Commercial useof PAM in agriculture started to grow in the mid-90's and has graduallyincreased to levels of several million pounds per year of annualapplication in the U.S. In current use, the copolymers are generallydissolved in irrigation water at doses of 2 to 10 ppm, which converts toabout 2 to 5 lbs per acre.

Principal benefits include soil retention and water conservation. Soilis retained on the fields via the agglomerating action of PAM as itflocculates soil constituents into larger, adhering particles thatsettle out of the flow. Hence, the water runs clear rather than turbiddown the furrow. Moreover, because the fine powders and platelets of thesoil become agglomerated as part of the settled particles, the naturalporosity of the soil along the furrow does not become clogged with thesefines as occurs in untreated furrows, and the infiltration of water intothe soil is improved. Thus, water is conserved on the field, rather thanflowing over and off the field, carrying topsoil with it. Ancillarybenefits include reduced loss of adsorbed nutrients, fertilizers, andtreatment chemicals such as herbicides and pesticides from the soil.These benefits lead to overall improvements in yields and crop quality.

On the other hand, there are problems with the ongoing usage of PAM inagriculture. For example, the polymers are generally very high MW (e.g.12 to 22 million Da), which makes them slow to dissolve in water andproduces very high viscosity solutions. Preparation of aqueous solutionsrequires vigorous stirring for extended periods to prevent the formationof viscous, gelatinous clumps, which remain insoluble and tend to clogmetering equipment and delivery systems. Handling issues of this naturehave significantly hindered the adoption of PAM by many growers.

In addition, the base monomer, acrylamide, is a hazardous, reactivemonomer that is a known neurotoxin and suspected carcinogen. Of course,effective steps are taken to ensure that residual levels of monomer inthe polymer products are well within safety limits. Nonetheless, it isevident that there are several properties and features of the copolymersof acrylate and acrylamide that are not desirable. Consequently,alternative materials are sought that will function well inagglomerating soil particles, without the handling issues and perceivedenvironmental problems associated with PAM.

Other flocculation technologies for which environmentally friendlyagents are sought include control of dust emissions into the atmospherefrom particulate surfaces, in locations such as rural roads,construction sites, temporary landing pads and strips, and outdoorarenas and facilities. Currently used dust control agents have also beenbased on copolymers of acrylate and acrylamides, as well as other vinylmonomers that are derived from feedstocks of natural gas andpetrochemicals (see e.g. U.S. Pat. Nos. 4,801,635, 5,514,412, and5,242,248). Similar materials are used for the very high volumecommodity markets for water treatment, including industrial andmunicipal water treatment (U.S. Pat. No. 5,178,774), treatment ofprocess waters during mining operations (U.S. Pat. Nos. 4,253,970,4,839,060, and 6,042,732), and treatment of municipal sewage andagricultural wastes for clarification and removal of suspended solids(U.S. Pat. No. 5,776,350).

A particular area in which improved flocculants are sought is in thearea of oil-sands mining and processing. In this process, as describedfurther below, roughly three barrels of oily and bituminous-containingprocess water are produced per barrel of oil. This process water iseventually recycled into the steam generators, but it must first beclarified and separate from substantial amounts of suspended andemulsified oil and bitumen. Because of the high oily and bituminouscontent of the process waters, ranging roughly from 1% to 60% solids,and the elevated temperatures involved (95° C. or higher), it has beenchallenging to design effective water-treatment protocols that clarifythe water and provide good separation of the aqueous and petrochemicalphases. Current practice for clarification of oil-sands process watertypically employs high levels (thousands of ppm or more) of inorganicsalts and/or polycationic agents, and take several hours, yet stilloften result in incomplete separation. Improved methods and compositionsfor clarifying such process waters are therefore desired.

SUMMARY

The compositions disclosed herein include amino acid copolymers,particularly copolymers of aspartate, asparagine, and/or succinimide,which may be crosslinked; polysaccharides, particularly starches andmodified starches; acrylamide polymers such as acrylamide/acrylatecopolymers; and polycationic polymers. These polymers, and particularlycombinations thereof, as described herein, have good flocculationproperties and are useful, for example, as soil retention and waterconservation agents during irrigation in agriculture; for settling ofsuspended solids in water, such as in settling ponds and sumps on farms,or in process waters from mining operations; and in dust control, forexample on roads, landing strips and pads, and at construction sites;among other uses. In some cases, the compositions may be modified toproduce dispersant, rather than flocculent, activity.

The amino acid polymers, which can be produced from polysuccinimide,have defined ratios of aspartate, asparagine, and/or succinimide, alongwith crosslinking agents in some cases. Also disclosed are variousmethods of production of these copolymeric materials, as well as thestarting polysuccinimides.

The modified carbohydrate polymers are made from naturalpolysaccharides, including starches and cellulosics. Modificationsinclude conversion to a partially soluble, activated form; attachment ofmonomeric substituents; and grafting of amino acid copolymers.

Consequently, it is useful that in the present invention, inexpensivebiological materials made from natural carbohydrates, amino acids, andtheir polymers are presented as flocculants, with particular utility assoil-retention and water-conservation agents. Moreover, formulations areidentified in which marked synergisms were observed between thebiological polymers and the current commercial standard flocculants, thecopolymers of acrylate and acrylamide. This discovery enables use ofhighly effective and economic formulations that include both thebiological polymers and the vinyl copolymers, these latter at much lowerdosing, if so desired. The formulations of the present invention alsoexhibit improvements in handling, due to decreased viscosity andtendency to gel as compared to traditional copolymer flocculants ofacrylate and acrylamide.

The disclosed processes for clarification of oil-sands process watersalso require much lower levels of active agents than currently usedmethods, while providing improved speed and efficiency of clarification.

OVERVIEW OF PREFERRED EMBODIMENTS

In one aspect, the invention provides a method of producing flocculationin a soil/water mixture, by applying to, or including in, the soil/watermixture, a composition comprising an activated starch and an acrylamidepolymer. The composition generally contains these components in a ratiobetween 0.1:1 and 100:1, preferably between 5:1 and 30:1, morepreferably between 5:1 and 10:1. The amount of the composition ispreferably about 0.2-300 ppm relative to said water in said soil/watermixture. Typically, amounts of about 0.35-100, preferably 0.5-50, morepreferably 0.75-30 ppm, relative to water in the soil/water mixture, areused. Levels of 1-10 ppm are generally found to be effective.

For example, the flocculating composition may be added to an aqueoussoil-containing suspension, preferably to obtain a concentration in theabove ranges, relative to water in the suspension. As another example,(water in) a soil furrow may be irrigated using water containing theflocculating composition, preferably in the above ranges ofconcentrations. In the latter case, it can be seen that the soil/watermixture is subjected to conditions of fluid flow, as in furrowirrigation of soil, or pressure from droplet impact and the resultingturbulence, in spray irrigation of soil. In preferred embodiments of theinvention, flocculation is effective under these conditions, resultingin improved soil retention and/or water infiltration during irrigation.The compositions can also be used for flocculation of municipal wastewater or industrial waste water.

The acrylamide polymer is preferably an acrylamide/acrylate copolymer,having about 50-95 mole %, preferably 70-90 mole %, and more preferablyaround 80 mole % acrylamide residues. The molecular weight of thecopolymer is preferably about 5 to 30 million, more preferably 12 to 25million, and most preferably 15 to 22 million Daltons.

The activated starch may be prepared by heating an aqueous suspension ofstarch for up to about 2 hours, preferably 0.5-2 hours, at a temperaturebetween 70° and 100° C., depending on the type of starch used. Forpotato starch, preferred temperatures are about 70-80° C., especially70-75° C.; for wheat starch or corn starch, preferred temperatures arebetween about 85° and 100° C., especially 90° to 95° C. The suspensionpreferably contains about 5-10 weight % or less of the starch in water.Preferably, the pH of the suspension is ≥7, e.g. about 6-7.

Alternatively, a starch suspension or slurry may be activated by rapidheating, such as exposure to steam for brief intervals, e.g. about 10seconds to 10 minutes, typically about 1-4 minutes, e.g. about 2-3minutes (jet cooking). Again, higher temperatures are typically used forwheat and corn starches, as described further below.

The flocculant compositions may be prepared by combining the activatedstarch suspension, after heating as described above, with an aqueoussolution of the acrylamide polymer. Alternatively, the acrylamidepolymer may be included in the suspension of native starch as the latteris activated in a manner described herein.

The combined weight % of starch and acrylamide polymer in the finalcomposition is typically about 0.1 to 50%, preferably 0.1 to 25%, morepreferably 0.5 to 15%, and most preferably 1% to 10%. In selectedembodiments, the combined weight % of starch and acrylamide polymer isabout 2 to 5%.

As described further herein, inorganic salts may be added to reduceviscosity, particular for more concentrated formulations. Preferably, apreservative, such as a biocidal or biostatic agent, is added to inhibitmicrobial growth or degradation of the starch.

The compositions may be prepared in a solid or semisolid form byremoving a majority of the water from an aqueous suspension of starchand/or acrylamide polymer, prepared by one of the methods describedherein. In one embodiment, this is conveniently done by heating at about80° C. The water may also be removed by other methods, such asspray-drying, freeze-drying, or solvent extraction. Preferably,temperatures >80° C. are avoided. Further to this aspect, the inventionprovides dry blends of activated starch, prepared by one of theactivation methods described herein and subsequently dried, andacrylamide polymers, such as PAM. Such blends may be added to soildirectly, followed by addition of water; or, more typically, they can bereformulated in water prior to use.

In one aspect of the invention, the activated starch compositions areemployed alone, without the acrylamide polymer, or with small amounts ofthe acrylamide polymer, and are effective to improve water infiltrationin soil during irrigation. Levels of amounts of about 0.2-50, morepreferably 0.3-30 ppm, in irrigation water can be used. Levels of 1-10ppm are generally found to be effective. In further embodiments, levelsof 3-10 or 5-10 ppm are used.

In a related aspect, the invention provides a method of flocculatingsuspended or emulsified particles in a mixture comprising such particlesand water, by applying to or including in such a mixture, a compositioncomprising a maleamate-modified polysaccharide, preferably amaleamate-modified starch. as described herein. Specifically, themaleamate-modified starch comprises groups of the form—CH(COO⁻M⁺)CH₂C(O)NH₂, linked to the starch via ether linkages, where M⁺represents hydrogen or a positive counterion.

The composition generally contains these components in a ratio between1:1 and 100:1, preferably between 2:1 and 20:1. The amount of thecomposition is preferably about 0.2-300 ppm relative to said water inthe treated mixture. Typically, amounts of about 0.3-100, preferably0.4-50, more preferably 0.5-30 ppm, relative to water, are used. Infurther embodiments, levels of 1-25 or 5-10 ppm are used.

The mixture may be a soil/water mixture, as described for otherflocculating starch/polymer compositions above. Alternatively, themixture could comprise municipal waste water or industrial waste water.They are particularly useful for mixtures subjected to conditions offluid flow or turbulence, e.g. for irrigation of soil in agriculturalsettings, and are effective to enhance soil retention under conditionsof such flow and/or pressure, as well as to enhance water infiltrationinto the soil.

In one embodiment, the composition further comprises an acrylamidepolymer, as described above, preferably copoly(acrylamide/acrylate) orPAM. Such compositions are typically effective as flocculants, soilretention agents, dust control agents, etc., at amounts about 25-50%less than required for activated starch/acrylamide polymer compositionsin which the starch is not maleamate-modified.

The composition may also be a ternary composition, further containingactivated starch, as described above. Such compositions are typicallyeffective as flocculants, soil retention agents, dust control agents,etc., at amounts about 50% less than required for activatedstarch/acrylamide polymer compositions without maleamate-derivatizedstarch. The maleamate-modified starch and activated starch are eachtypically present at a level about 2-10 times, more typically about 5-10times, that of the acrylamide polymer, by weight.

These compositions can be prepared as aqueous suspensions, e.g. bycombining a suspension of activated starch with the maleamate-modifiedstarch and the acrylamide polymer, in an aqueous medium. They may alsobe prepared in solid or semisolid (i.e. dried) form, as described forthe starch/acrylamide polymer compositions above, and either applied indried from or reconstituted prior to use.

Also provided is a method for preparing a polysaccharide modified with agroup selected from maleamate and maleate, by treating thepolysaccharide in water, at a basic pH, with a maleamate salt and/or amaleate salt, effective to produce a polysaccharide comprising groups ofthe form —CH(COO⁻M⁺)CH₂C(O)Z, linked to the polysaccharide via etherlinkages, where M⁺ represents hydrogen or a positive counterion, and Zrepresents NH₂ or O⁻M⁺.

Accordingly, the invention further provides a modified polysaccharidecomprising groups of the form —CH(COO⁻M⁺)CH₂C(O)Z, linked to thepolysaccharide via ether linkages, where M⁺ represents hydrogen or apositive counterion, and Z represents NH₂ or O⁻M⁺. In one embodiment,the salt is a maleamate salt, such that Z represents NH₂. In anotherembodiment, the salt is a maleate salt, such that Z represents O⁻M⁺. Thetwo may also be used in combination.

The polysaccharide is preferably a starch, e.g. potato, wheat or cornstarch, but may also be selected from other polysaccharides such asagar, carrageenan, chitosan, carboxymethyl cellulose, guar gum,hydroxyethyl cellulose, gum Arabic, pectin, and xanthan gum.

The method may also be adapted to modify such polysaccharides with othergroups, via Michael addition of hydroxyl groups of the polysaccharide toa molecule having a conjugated double bond. Preferably, the conjugateddouble bond is flanked by two conjugating groups selected fromcarbon-carbon and carbon-oxygen double bonds, where at least one is acarbon-oxygen double bond. Alternatively, the molecule includes a fattyalcohol component, e.g. a fatty alkyl or alkenyl acrylate (where “fattyalkyl or alkenyl” refers to a saturated or unsaturated, respectively,acyclic hydrocarbon radical which is preferably linear and contains sixto about 24 carbon atoms; examples are stearyl and oleyl).

It is found that the maleate-modified starches are useful asdispersants, scale inhibitors, and chelators. Accordingly, the inventionfurther provides a method of promoting dispersion of suspended oremulsified particles in a mixture comprising said particles and water,said method comprising: applying to, or including in, said mixture, acomposition comprising a maleate-modified polysaccharide, preferably amaleate-modified starch. The maleate-modified starch comprises groups ofthe form —CH(COO⁻M⁺)CH₂COO⁻M⁺, as described above, linked to the starchvia ether linkages, where M⁺ represents hydrogen or a positivecounterion.

In another aspect, further pertaining to preparation of flocculatingcompositions, a method is provided for preparing a crosslinkedaspartate/asparagine copolymer, by adding a crosslinker, preferablyselected from polyols and polyamines, to an aqueous solution of a watersoluble aspartate/asparagine copolymer. The resulting solution is dried,e.g. at about 60-80° C. for several hours, and the residue is heated,preferably at about 170-180° C. for about 3 hours, under vacuum or in aninert atmosphere.

The molar ratio of monomeric residues in the starting copolymer(including both Asp and Asn) to crosslinker is in the range of about 1:1to 100:1; in selected embodiments, from 4:1 to about 35:1 or from 2:1 toabout 35:1. Preferably, higher levels of crosslinker are employed forlower MW copolymers, and vice versa. The crosslinker is preferablyselected from diols, triols, and diamines; more particularly from C2-C8alkanediols, C3-C8 alkanetriols, C2-C8 alkanediamines, and lysine.Exemplary crosslinkers include α,ω-diamines such as ethylenediamine andhexamethylenediamine. Also included are polymeric crosslinkers such aspolylysine, typically of low molecular weights (1 to 10 kDa), althoughmolecular weights up to about 70 kDa have been used.

The aspartate/asparagine copolymer to be crosslinked preferably has aresidue ratio of aspartate/asparagine of about 1:3 to 1:10; in oneembodiment, the copolymer is about 80 mol % asparagine. Its molecularweight is preferably about 600 to 300,000 Daltons, more preferably about5,000 to about 50,000 Daltons.

Exemplary crosslinked copolymers include: a crosslinkedaspartate/asparagine copolymer having a molecular weight of about 600 toabout 300,000 Daltons, preferably 5 to 50 KDa, and a residue ratio ofaspartate to asparagine (including crosslinked residues) of about 1:1 to1:10 or less, e.g. about 1:4, which is crosslinked with a crosslinkerselected from a diol, a triol, and a diamine. In selected embodiments,the crosslinker is selected from C2-C8 alkanediols, C3-C8 alkanetriols,C2-C8 alkanediamines, lysine, and polylysine; preferably, thecrosslinked is selected from 1,6-hexanediamine, ethylenediamine, andlysine. In other selected embodiments, the molecular weight of thecopolymer is about 30 KDa, the crosslinker is selected from C2-C8alkanediols, C3-C8 alkanetriols, C2-C8 alkanediamines, and lysine, andthe molar ratio of monomeric residues in the copolymer to crosslinker isin the range of about 2:1 to 100:1, preferably 15:1 to 40:1. Preferably,the crosslinker is 1,6-hexanediamine.

The crosslinked aspartate/asparagine copolymer may also be prepareddirectly from polysuccinimide. An aspartate/asparagine copolymer havinghigh mole % asparagine is prepared by combining, at a temperature ofabout −20° to 5° C., a mixture of polysuccinimide in water with NH₄OHand a crosslinker as described above, stirring the resulting mixtureuntil substantially all solids are dissolved, and drying the resultingsolution, e.g. at about 60-80° C. for several hours. The NH₄OH istypically added in a molar excess of twofold or more. Thepolysuccinimide and copolymers thereof, e.g. aspartate/succinimide oraspartate/asparagine copolymers, may be prepared by methods known in theart and/or by methods disclosed herein.

The crosslinked copolymers as described above may be used, as shownherein, for flocculating suspended or emulsified particles in a mixturecomprising such particles and water, by applying the crosslinkedcopolymers to, or including them in, such as mixture. The mixture may bea soil/water mixture, e.g. in agricultural uses such as soil retentionand water infiltration. The crosslinked copolymer may be used incombination with other flocculating materials described herein,including activated starch, maleamate-modified starch, and/or anacrylamide polymer.

These compositions can be prepared as aqueous suspensions, e.g. bycombining a suspension of activated starch with the further component(s)in an aqueous medium. They may also be prepared in solid or semisolid(i.e. dried) form, as described for the starch/acrylamide polymercompositions above, and either applied in dried from or reconstitutedprior to use.

As discussed above, the agents disclosed herein are useful, alone orpreferably in the combinations particularly described, for flocculation,soil retention, and water infiltration agents. Although agriculturalapplications are particularly contemplated, they may also be used, forexample, in processing of waste waters from municipal and industrialsources. One particular embodiment involves treatment of process watergenerated in mining operations. Adding a flocculating composition asdisclosed herein, preferably comprising an activated starch and/or amaleamate-modified starch in combination with an acrylamide/acrylatecopolymer, and/or a crosslinked copolymer as described herein, iseffective to flocculate emulsified or suspended materials in suchprocess waters.

The emulsified or suspended materials may include minerals orhydrocarbon residues; the latter are especially prevalent in waste waterfrom mining oil sands. In a method of clarifying hydrocarbon- andbitumen-containing process water obtained from an oil-sands miningoperation, a composition comprising an acrylamide copolymer is added tothe process water. The acrylamide copolymer is an anionic acrylamidecopolymer, such as an acrylamide/acrylate copolymer, or, in a preferredembodiment, a cationic acrylamide copolymer (“cationic PAM”), such as anacrylamide/allyl trialkyl ammonium copolymer or an acrylamide/diallyldialkyl ammonium copolymer. Exemplary copolymers include anacrylamide/allyl triethyl ammonium copolymer or acrylamide/diallyldimethyl ammonium copolymer. In each case, the mole % acrylamide is atleast about 50%, preferably at least 70%, and more preferably about80-90%. The molecular weight of the acrylamide copolymer is at least 1million Daltons, and preferably at least 4 million Daltons.

Preferably, the flocculant composition further includes an activated ormaleamate-modified starch, preferably an activated starch; i.e. a heatactivated starch as described herein. These components may be present ina ratio of activated starch:acrylamide copolymer of about 0.1:1 to100:1, e.g. about 0.5:1 to 10:1.

In a further preferred embodiment, a polycationic coagulant is alsoadded to the process water, together with or, more preferably, prior toaddition of the acrylamide copolymer and/or activated starch. In thisembodiment, the acrylamide copolymer is preferably a cationic acrylamidecopolymer. An exemplary polycationic coagulant is polyEPI/DMA (acopolymer of epichlorohydrin and dimethylamine). Other coagulantsinclude polymers of cationic monomers such as, for example, ammoniumalkyl (meth)acrylamides, ammonium alkyl (meth)acrylates, diallyldialkylammonium salts, allyl trialkyl ammonium salts, and amino acidssuch as lysine or ornithine. The mole percent of the cationic monomer isat least 50%, and other monomers, if present, are neutral monomers, e.g.acrylamide. The molecular weight of the polycationic coagulant ispreferably at least 5000, and may be up to 100,000 or more, but istypically less than 1 million Daltons.

Preferably and advantageously, the process water is acidified prior toaddition of the polymeric agents, e.g. to a pH of about 2 to 4.

In general, the total amount of active additives used in the process isin the range of 2 to 500 ppm, preferably 2 to 100 ppm, more preferably 2to 75 ppm. In a preferred method, employing pH adjustment, apolycationic coagulant, and a starch/cationic PAM flocculant, asdescribed above, the total amount of active additives is preferably inthe range of about 2 ppm to about 60 ppm relative to the process water.When the starch is not included, an amount in the range of about 5 ppmto about 100 ppm relative to said process water is typically employed;and when no pH adjustment is done, an amount of 5 ppm to about 500 ppmrelative to said process water is typically employed.

The coagulant and flocculant may be used in approximately equal amounts.Alternatively, they may be used in a ratio of up to about 2/1 flocculantto coagulant, or vice versa. Other ratios may also be used as effective.

The invention thus provides a clarification process for oil- andbitumen-containing process waters from oil-sands mining, preferablycomprising the steps of:

(a) adjusting the pH of the process water to about 2-4;

(b) adding a polycationic coagulant, preferably polyEPI/DMA, to theprocess water; and

(c) adding a flocculant composition, comprising a high MW cationicacrylamide copolymer, preferably an acrylamide/allyl triethyl ammoniumcopolymer or acrylamide/diallyl dimethyl ammonium copolymer, and anactivated starch, to the process water. The acrylamide copolymer has amole % acrylamide of at least 50% and a molecular weight of at least 1million Daltons; the polycationic coagulant has a mole % cationicmonomer of at least 50% and a molecular weight of at most 1 millionDaltons.

The process preferably allows a flocculated layer of oily and/orbituminous material to be removed from the top surface of a clarifiedlayer of the process water.

In a typical process, the process water is initially at a temperature of85° C. or higher, and it contains 1-60 weight percent bitumen and otherhydrocarbons. The process is thus effective on process watershaving >20%, >30%, >40%, and >50% by weight bitumen and otherhydrocarbons, as is typical of downstream waste waters from oil-sandsmining processes.

A related process for clarifying hydrocarbon- and bitumen-containingprocess water obtained from an oil-sands mining operation includes thesteps of

(a) adjusting the pH of the process water to about 2-4; and

(b) adding a polycationic coagulant, such as described herein, to theprocess water. The amount of polycationic coagulant, preferablypolyEPI/DMA, added is preferably about 10 ppm to about 100 ppm relativeto the process water. This process is less efficient than processesincluding the flocculant composition described above but can still beeffective in clarifying process waters.

In a related aspect, the invention provides a composition for use inclarifying hydrocarbon- and bitumen-containing process water obtainedfrom an oil-sands mining operation. The composition consists essentiallyof (i) polyEPI/DMA and (ii) a cationic acrylamide copolymer, preferablyan acrylamide/allyl trialkyl ammonium copolymer or an acrylamide/diallyldialkyl ammonium copolymer. The cationic copolymer has a molecularweight of at least 1 million and contains at least 50 mole % acrylamide;preferably, the molecular weight is at least 4 million, and mole %acrylamide is 80-90%. A further composition for use in clarifyinghydrocarbon- and bitumen-containing process water obtained from anoil-sands mining operation comprises (i) polyEPI/DMA, (ii) a cationicacrylamide copolymer as described above, and (iii) an activated starch,such as described herein.

Another useful application of the flocculating agents disclosed herein,used alone or in the combinations particularly described, is in the areaof dust control. Accordingly, a flocculating composition as disclosedherein, preferably comprising an activated starch and/or amaleamate-modified starch in combination with an acrylamide/acrylatecopolymer, and/or a crosslinked copolymer as described herein, isapplied to a particulate surface, such as a road, preferably incombination with water. Various polysaccharides, in addition to starch,are found to be useful for this purpose, including agar, carrageenan,chitosan, carboxymethyl cellulose, guar gum, hydroxyethyl cellulose, gumArabic, pectin, and xanthan gum.

Also disclosed herein are various methods of preparing polysuccinimidesand amino acid copolymers, which can be used, as described above, inpreparing flocculating compositions.

For example, a method is provided that is effective to preparepolysuccinimides having molecular weights up to about 300,000. In thismethod, polyphosphoric acid is mixed with water, and aspartic acid isadded to the mixture to form a slurry, in an amount such that thephosphoric acid is present at 0.5 to 100% by weight of the asparticacid. In one embodiment, the volume of water mixed with thepolyphosphoric acid is approximately equal to the volume of the asparticacid when dry. The slurry is allowed to sit at ambient temperature forup to an hour and is then dried, e.g. by heating at about 80-150° C., orvia spray drying, forced air, vacuum, or solvent extraction. (For dryingand/or concentration of aqueous reagent mixtures as described herein,any suitable oven, drier, evaporator, spray-drier, distillation,solvent-extraction or other method of removal of water can generally beused in this step of concentrating and drying. The drying step may beaccomplished by any method known in the art, e.g. simple heating byconvection, mild heating by forced air, spray drying, freeze drying, andothers.) The dried material then is heated to polymerize, at about150-240° C., preferably 180-220° C., under vacuum or in an inertatmosphere such as a nitrogen stream, typically for about 4 hours.

Accordingly, the method can be used to provide a polysuccinimide polymerhaving a molecular weight of at least 200 kDa, preferably at least 250kDa, and having a substantially linear morphology.

Also provided are methods for preparing low molecular weightaspartate/succinimide copolymers, preferably having a high molepercentage of succinimide residues. In one method, a solution of sodiumaspartate and ammonium aspartate in water, preferably at a molar ratioof about 1:10, more preferably about 1:3, is acidified, preferably to apH of 3 to 5.5. The solution is then dried, e.g. by heating at about120° C.; and the residue is heated at 160-220° C. for about 1 to 8 hoursunder vacuum or in an inert atmosphere.

This copolymer can then be converted, if desired, to a low molecularweight aspartate/asparagine copolymer, by treating with aqueous NH₄OHand drying the solution, preferably at about 60° C. Finally, a lowmolecular weight Asp/Asn/succinimide terpolymer can be produced byacidifying an aqueous solution of the aspartate/asparagine copolymer,e.g. to about pH 4, drying the solution, preferably at about 60° C.-80°C., and heating the residue at about 170-180° C. under vacuum or aninert atmosphere.

In another method for preparing a low MW aspartate/succinimidecopolymer, NH₄OH and a water soluble alkali or alkaline earth salt, suchas, for example, MgSO₄, NaCl, Na₂SO₄, CaCl₂, etc., are added to anaqueous solution of aspartic acid; the resulting solution is dried asdescribed above, and the residue is polymerized by heating at about160-240° C., preferably 180-220° C., for about 1 to 8 hours under vacuumor in an inert atmospheres. The molar ratio of the added salt to NH₄OHcan vary from about 1:100 to 100:1, depending on the desiredaspartate/succinimide ratio in the product copolymer.

As above, the aspartate/succinimide copolymer can be converted to anaspartate/asparagine copolymer, by ring opening with aqueous NH₄OH,followed by drying under non-hydrolytic conditions at about 80° C. Thiscopolymer can in turn be converted to anaspartate/asparagine/succinimide terpolymer, by acidifying an aqueoussolution of the copolymer, to about pH 3 to 5.5; drying the solutionunder non-hydrolytic conditions at about 60-80° C.; and heating theresidue at about 170-180° C., under vacuum or in an inert atmosphere,for about 1-3 hours.

Such terpolymers are useful for grafting to starch or otherpolysaccharides, to produce flocculants as described herein. This can beaccomplished by combining a suspension of starch, preferably activatedas described above, with the terpolymer, adjusting the pH to about 9-12,allowing the solution to react for up to about 3 hours, and neutralizingthe solution with acid.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1. Soil-cuvette assay representative results, carried out asdescribed in Example 26b. Control treatments contain 25 mg soil in 10 ml0.1 M CaCl₂, no additive. All other treatments contain equivalent doses(0.667 ppm) of copoly(acrylic, acrylamide) (PAM), which is justsufficient to provide a small benefit in rate of settling of soilparticles. The “PL” treatments, in an embodiment of the invention,further include 3.33 ppm activated starch, a dose that by itself has nobeneficial effect on settling of the soil particles. Hence, the resultsdemonstrate the synergism between PAM and the activated starch. (Thedifferent PL preparations contain different preservatives, as describedin Section V.A below.)

FIGS. 2A-B. Static water-infiltration representative results, carriedout as described in Example 28a. Control treatments consisted ofinfiltration of soil with tap water. The PAM and PL treatments eachincluded 2 ppm PAM, while the PL treatments further included 10 ppmactivated starch (in FIG. 2A, formula 1=suspension activated; formula2=ColdSwell™ 1111 provided by KMC, Denmark). FIG. 2B also includestreatment with 10 ppm activated starch alone. In the PL treatments, thewater infiltrated to significantly greater depths significantly fasterthan did control and PAM treatments, as shown.

FIGS. 3-5. Representative dynamic water infiltration results, carriedout as described in Example 28b, using the formulation designated “PLformula 2” in FIG. 2A. Figures show rate of surface water lateraladvance; time of infiltration to increasing depths; and surface wateradvance versus infiltration depth, respectively. Water treated with thisformulation advanced laterally along the surface more quickly (FIG. 3),infiltrated to greater depths more quickly (FIG. 4), and infiltrated togreater depths for a given amount of lateral advance (FIG. 5) than incontrol treatments with no additive. (Some of these figures suggest thatthe control data began to converge with the PL data after about 80 cmlateral advance or 8 cm depth. This observation is an artifact of theexperimental setup; at this point, the water had reached the bottom ofthe plastic support in the test apparatus and began to flow quicklyalong the support.)

FIG. 6. Effect of ammonium sulfate ((NH₄)₂SO₄) concentration onviscosity of an activated starch/PAM formulation. (NH₄)₂SO₄concentrations are given as % by weight of the total aqueous starch/PAMformulation (e.g., PL 4.5% composed of 3.75% by weight activated starchand 0.75% by weight PAM in water).

FIG. 7. Schematic of the minifurrow apparatus containing 200 g of soil.Upper image: A. Polyethylene furrow (6 ft) attached to wooden support.B. Inflow holder (foam core) with silicone tubing. C. Peristaltic pump.D. Reservoir on a magnetic stirplate. E. Toploading balance. F. Inclinedholder (foam core) set at 10 degrees. G. Outflow holder with funnel and20-ml vial.

FIG. 8. Representative results of experiments using the apparatus ofFIG. 7, in which the first 20 ml of outflow was collected in vials. Inthe control treatment, the initial outflow contained approximately 50%by volume eroded soil. In treatments that were fully stabilized by PAM(PAM full; depending on flow rates and slope, the doses ranged from 0.5to 10 ppm), there was little or no sediment in the outflow. Treatmentsat intermediate doses (PAM partial; e.g. 0.75 ppm) gave intermediatelevels of eroded soil in the initial outflow, e.g. 10 to 40% by volume.By comparison, the activated starch/PAM (here designated as SS PL, at aPAM dose equivalent to ⅔ of the above “PAM partial” treatment) andactivated starch/starch-maleamate/PAM (designated SS PL Plus, using %the PAM dose of the SS PL treatment) also stabilized the soil in theminifurrow completely so that there was little or no sediment in theinitial outflow. (See further description in Section V.B below andExample 27.)

FIG. 9. Schematic of the static water-infiltration apparatus. A. 5-mlpipettor for addition of the water plus soil suspension, the first 5 mljust having been added. B. Clear acrylic tube, 1 inch inner diameter, 12inches height, containing 195 g of soil. C. Reservoir of water,containing 5 g of soil, on magnetic stirplate. D. Outflow, having filterpaper taped to the column to hold the soil in place. E. Stop watch.

FIG. 10. Schematic of the dynamic water-infiltration apparatus, theinfiltration plexirill. A. Peristaltic pump. B. Reservoir. C. Clearacrylic furrow, 6 ft length, 6 inches depth, 1 inch inner width, plus 8kg soil. D. Receiving vessel plus toploading balance. (See Example 28.)

DETAILED DESCRIPTION I. Definitions

The terms below, as used herein, have the following definitions, unlessindicated otherwise:

“Molecular weight” of a polymer refers to weight average molecularweight as determined by gel permeation chromatography (GPC), preferablyusing commercially available polymers e.g. polyaspartate, polyacrylate,copoly(acrylate/acrylamide), or polysaccharides, such as dextrans, asstandards.

“Substantially linear” with reference to a polymer backbone indicatesthat the backbone has at most one branch point per six monomer residues,preferably at most one per 12 residues, and more preferably at most oneper 20 residues, on a random basis.

“Water soluble” indicates that a polymer is greater than 95%, andpreferably greater than 99%, soluble in water at room temperature.

An “aspartate residue”, as used herein, includes backbone residues ofthe form CH(COOR)—CH₂—(C═O)—NH— or —CH(CH₂COOR)—(C═O)—NH— (β and αforms, respectively), where R is hydrogen, a cationic counterion, or, inderivatized copolymers, a substituent. The term thus includes asparticacid residues as well as metal or ammonium aspartate residues.

An “asparagine residue”, as used herein, includes backbone residues ofthe form CH(CONH₂)—CH₂—(C═O)—NH— or —CH(CH₂CONH₂)—(C═O)—NH— (β and αforms, respectively).

The term “polymer” encompasses homopolymers, copolymers, terpolymers,etc. The term “copolymer” refers to a polymer having more than one typeof monomer residue. The term “terpolymer” refers to a polymer having atleast three, and typically exactly three, types of monomer residue.

An “aspartate/succinimide copolymer”, as defined herein, containsresidues of aspartate and succinimide, and may further contain 50 mole %or less, preferably 10 mole % or less, of other monomer residues.Similarly, an “aspartate/asparagine copolymer”, as defined herein,contains residues of aspartate and asparagine, and may further contain50 mole % or less, preferably 10 mole % or less, other monomer residues.Similarly, an “aspartate/asparagine/succinimide terpolymer”, as definedherein, contains residues of aspartate, asparagine, and succinimide.Such polymers may further contain 50 mole % or less, preferably 10 mole% or less, other monomer residues. In selected embodiments, theserespective copolymer types contain only the named monomer residues. (Theaspartate residues may contain a positive counterion, such as sodium orammonium, or be protonated, depending on pH.)

terpolymer of aspartate, asparagine, and succinimide

An “acrylamide polymer” or “acrylamide copolymer” refers to a polymercontaining acrylamide monomer residues, preferably at a molar ratiogreater than 50%, more preferably at a molar ratio greater than 75%.Examples include acrylamide homopolymer (polyacrylamide) orcopoly(acrylate/acrylamide). Unless otherwise indicated, “PAM” refers tocopoly(acrylate/acrylamide), preferably having these two monomers in aratio of 1:3 to 1:5, preferably about 1:4. A “cationic PAM” is acopolymer of acrylamide with a cationic monomer.

“Starch” refers generally to a carbohydrate polymer stored by plants;common examples are potato, corn, wheat and rice starch. It is in fact amixture(s) of two polymers: amylose, a linear (1,4)-α-D-glucan, andamylopectin, a branched D-glucan with primarily α-D-(1,4) and about 4%α-D-(1,6) linkages. Native (unmodified) starch is essentially insolublein water at room temperature.

The phrase “activated starch” refers to a partially solubilized form ofstarch prepared by heating starch in water, e.g. in a suspension orspray, preferably at a temperature less than 100° C., e.g. 70-95° C., asdescribed further below. Such activation typically provides flocculationactivity not observed in the native (non-activated) starch. The termalso encompasses commercially available pregelatinized starches,especially ColdSwell™ starches provided by KMC (Denmark).

A “soil/water mixture” refers to an aqueous liquid having suspendedsolids, as found in agriculture, mining, and sewage treatmentoperations. In one embodiment, the term refers to irrigated soil inagriculture, including furrow irrigation (where water is flowed over thesoil) or spray irrigation (where water impacts the soil from above).Agricultural settling ponds are also included. In another embodiment,the term refers to waste waters from mining operations. In thesoil/water mixture, either the solid (soil) or the liquid may be presentin excess.

The term “alkyl” refers to saturated hydrocarbon radicals up to about 8carbons in length, and preferably refers to lower alkyl, i.e. C1 to C6,more preferably C1 to C4. Specific embodiments include methyl, ethyl andpropyl (n-propyl or isopropyl). In particular embodiments, alkyl ismethyl or ethyl.

II. Modifications of Starch and Other Polysaccharides

The starch-based materials described herein are excellent flocculants,with good initial activity and increased activity with time, thusproviding a form of controlled-release activity. They perform very wellas compared to PAM in static flocculation assays. Under conditions ofturbulence or fluid flow, they significantly improve the performance ofreduced amounts of PAM as soil retention agents, as described furtherbelow. In addition, they significantly enhance water infiltration duringirrigation, where PAM alone has little or no apparent benefit.

A. Thermal Activation

Native starch, e.g. potato starch, corn starch, or wheat starch, is notwater-soluble and does not exhibit activity as a flocculent. However, itcan be modified via an aqueous thermal treatment that renders itpartially water-soluble and partially gelled, with some portiongenerally remaining insoluble. Any starch may be used; however, potatostarch is preferred with respect to (its) greater ease of solvation andlower activation temperature in comparison to other starches, such ascorn starch and wheat starch. Alternatively, use of other starches suchas corn or wheat starch, which are significantly less costly than potatostarch, is preferred in cases in which cost is the overriding concern.

Commercially available pregelatinized starch products, in particularColdSwell™ starch as provided by KMC (Denmark), may also be used. Othercommercially available cold water soluble starches that are useful inthe formulations and methods disclosed herein include Mira Sperse® 629corn starch (Tate & Lyle, Decatur Ill.), NSight™ FG-1 corn starch (AlcoChemical, Chattanooga, Tenn.), and Pregel™ 46 wheat starch (MidwestGrain Products, Atchison, Kans.).

In a typical activation procedure, such as described in Example 12a,potato starch is slurried in water at room temperature, preferably at aconcentration of about 2 to 4% by weight. The slurry is heated, withvigorous stirring, to about 60-80° C., preferably about 70-80° C., andmore preferably 70-75° C., for up to 2 hours, preferably 0.5 to 2 hours.Activation is generally carried out at near-neutral pH, e.g. about 6-7,preferably at slightly acidic pH, e.g. about 6.3 to 6.8. The optimaltemperature of activation generally depends on the type of starch beingused. For example, in the case of potato starch, as described above,activation begins at approximately 60° C., and inactivation occurs atapproximately 85° C. In the case of corn or wheat starch, activationrequires heating to 85 to 95° C., and inactivation occurs if thematerial is boiled. These latter types of starches are preferred inapplications which may involve exposure to higher temperatures, sincethey are generally more heat stable than potato starch.

Starch may also be activated via rapid heating, e.g. using steam forbrief intervals, as described in Example 12b. Accordingly, thecomposition is exposed to steam for about 10 seconds to 10 minutes,typically 1-4 minutes, more typically 2-3 minutes. Again, highertemperatures are generally employed for activation of corn and wheatstarch than for potato starch.

Upon activation, the starch becomes partially solubilized and partiallygelled, with some residual micron-sized particulates (visible via lightmicroscopy or atomic force microscopy). Starch activated in this manneris an effective flocculant in itself, particularly in fluids held underrelatively static conditions. In combination with other flocculatingmaterials, such as acrylamide polymers or amino acid polymers (e.g.copoly(asp/asn)), as described below, it forms synergistic compositionswhich are effective in stabilizing particles, such as soil, under fluidflow. For example, the soil retention activity of such a combination issignificantly greater than that of either component alone.

In addition, the activated starches exhibit increased flocculationactivity with time. In some cases, for example, the flocculationactivity is minimal when the material is first added to a soilsuspension, but becomes quite pronounced over a period of several daysor more. For example, as described in Example 12a below, the initialactivity of an activated starch at 30 μg/ml was roughly equivalent tothat of a commercial PAM at 10 μg/ml, but after a few days incubation ofsoil suspension plus additive, the activated starch, even at the lowerdoses (e.g. 5-10 μg/ml), outperformed this level of PAM. This activityoften persisted for several months before beginning to fade. Withoutbeing bound to a particular mechanism of action, this effect could bedue to slow solubilization of the gelled phase, and later any insoluble,ungelled globules of the activated starch, in the presence of water,releasing more molecules of the flocculating form of the starch. Thisfeature would add a level of sustained release to flocculation and soilretention compositions. Accordingly, the activated starch-containingflocculants can become increasingly more effective over time after theyare released into a fluid stream, e.g. during the time course of anirrigation or subsequent irrigations. The activity of the products,alone (and/)or in combination with other polymers, as flocculants, soilretention agents, water infiltration agents, and dust control agents isdescribed further below.

Multicomponent flocculant compositions, containing, for example,activated starch and an acrylamide copolymer, may be prepared bycombining an activated starch suspension, either commercially providedor heat activated as described above, with an aqueous solution ofacrylamide polymer.

Alternatively, the acrylamide polymer may be included in the suspensionof starch as the latter is activated in a manner described herein. Forexample, the composition may be prepared by first dispersing the starchin water at a temperature below the gelling temperature of the starch,then adding the acrylamide polymer, with vigorous stirring, to quicklydisperse the polymer before it begins to gel. Preferably, acrylamidecopolymer is added to an aqueous starch dispersion as a continuousstream of dry, granular material with vigorous stirring over an intervalof 2 seconds to 5 minutes, preferably 10 seconds to 1 minute, mostpreferably 15-40 seconds. The resulting suspension is then heated in amanner described above, e.g. by conventional heating or by jet cooking,to activate the starch while the acrylamide polymer dissolves. SeeExample 12B below for a representative process.

B. Chemical Derivatization

Derivatization of polysaccharides, such as starch, with maleamic acid isfound to enhance flocculant activity. Such derivatization of starchproduces a modified starch having pendant secondary amide groups ofmaleamide. It is believed that the grafted maleamide groups improveflocculation activity by increasing water solubility while retaining oreven increasing hydrogen bonding. Other polysaccharides that may besimilarly derivatized include, for example, agar, carrageenan, chitosan,carboxymethyl cellulose, guar gum, hydroxyethyl cellulose, gum Arabic,pectin, and xanthan gum.

In one embodiment, starch is derivatized via a Michael addition betweenthe hydroxyl groups of the glucose residues of starch and the doublebond of maleamic acid, forming a carbon-to-oxygen (ether) covalent bond.In a typical procedure, a suspension of potato starch at 2 to 4% byweight in water is reacted with an amount of maleamic acid to provide 1mole of maleamic acid per mole of glucose residue.

Effective reaction(s) conditions are basic pH, e.g. 9-13, preferablyabout 12-13, at about 60-125° C., preferably 70-95° C., for about 0.5-3hours, preferably about 1 hour. A pressure reactor may be used. It isalso useful to react higher residue ratios of maleamic acid to glucose,for example up to 3:1, under more alkaline conditions, for example up topH 13. An exemplary procedure is described in Example 14.

The starch-maleamate grafts so produced were very good flocculants thatalso could be formulated with amino acid or acrylamide copolymers, aswell as with ungrafted activated starch, to produce excellentsoil-retention agents. For example, the product of Example 14, assessedby the soil vial and soil rill assays described in Examples 26-27, wereexcellent flocculants in the former, with increasing activity over therange of 5, 10, and 30 μg/ml of soil suspension. In addition,flocculation activity increased remarkably with time, showing resultssuperior to PAM after a few days during which the soil suspension plusadditive was incubated. This activity persisted for several monthsbefore beginning to fade. The maleamate-modified starches were lesseffective as soil retention agents, as evaluated in the soil rill assaydescribed below, than as flocculants in static systems, but theyoutperformed activated underivatized starch in this respect.

Activated starch may also be derivatized with maleate, in a similarprocess using maleic anhydride or acid, as described in Example 15.These compositions exhibit marked dispersive activity rather thanflocculation activity, and thus can be used as dispersants, chelators,scale control agents, etc.

The method may also be adapted to modify such polysaccharides with othergroups, via Michael addition of hydroxyl groups of the polysaccharide toa molecule having a conjugated double bond. Preferably, the conjugateddouble bond is flanked by two conjugating groups selected fromcarbon-carbon and carbon-oxygen double bonds, where at least one is acarbon-oxygen double bond. Alternatively, the molecule includes a fattyalcohol component, e.g. a fatty alkyl or alkenyl acrylate.

III. Formulations of Polysaccharides with Acrylamide Co-Polymers orAmino Acid Co-Polymers

The activated and/or modified polysaccharides described above can becombined with other flocculating polymers to form synergisticcombinations; that is, where the activity of the combination issignificantly improved over the expected additive effect from thecomponents alone. For example, soil retention properties of smallamounts of copoly(acrylamide/acrylate) (PAM) are significantly improvedby addition of amounts of activated starch which, when used alone, showlittle activity in this area. Activated starch/PAM combinations alsoshowed significant improvements in water infiltration, where PAM alonehas no apparent effect.

A. Compositions with Acrylamide Polymers

Formulations containing activated and/or modified starch as describedherein, in combination with copolymers of acrylate and acrylamide, areemployed for flocculation, extending to improved soil retention, waterinfiltration, dust control, and clarification of oil sands processwaters, as discussed in Section VI below. In this latter application,cationic copolymers may be preferred. In preferred anionic PAM polymers,as generally employed in the agricultural processes described herein,the molar ratio of acrylate/acrylamide is about 1:4; molecular weightsare in the range of 12 million Da and higher, e.g. 18 to 22 million DA;and the polymers are predominantly linear. Such polymers are readilyavailable from commercial sources. Commercially available anionic PAMcopolymers that are useful in the formulations and methods disclosedherein include, for example, Superfloc® A836 and A-110 (Cytec, WestPaterson, N.J.), Flowpam™ AN 923 SH and AN 910 SH (SNF Inc., Riceboro,Ga.), and Soilfix® IR (Ciba, Tarrytown, N.Y.). Each of these productshas a molecular weight of at least 12 million Daltons and at least 80mole % acrylamide.

It is found that the levels of copoly(acrylate/acrylamide) required foreffective flocculation and soil retention are substantially reduced whencombined with modified starches as described herein, even when theamount of modified starch added, used in isolation, provides relativelysmall or even negligible benefits. This reduction in the amount of PAMemployed results in improved economics and better environmental andhealth profiles.

For example, combinations of activated starch:PAM in ratios ranging from10:0.3 to 10:5 were prepared as described in Example 16. Theseformulations were assessed for flocculation activity via the soil vial,soil cuvette, and soil rill assays described in Examples 26-27. Inaddition, field assessments in both furrow irrigation and sprayirrigation were run in some cases.

The combinations provided excellent flocculation and/or soil retentionat doses at which the activated starch alone or the PAM alone exhibitedlittle or no activity. Flocculation activity in the various assays wasgood at doses of 1 to 30 ppm with ratios up to 30:1 of activatedstarch:PAM. In the field work, the formulation of activated starch andPAM at ratios of 10:1 and higher performed at parity to PAM atequivalent doses, even though the actual dose of PAM was up to ten-foldlower in the synergistic formulation. The combinations also providedgreatly improved water infiltration, where even higher doses of PAMprovided no apparent benefit.

Combinations of activated maleamate-derivatized starch with PAM, also inratios ranging from 10:0.3 to 10:5, were prepared as described inExample 17. In the soil vial (static; flocculation) and soil rill (fluidflow; soil retention) assays, this formulation performed very well atdoses at which the control treatments (no additive, starch-maleamatealone, or PAM alone) exhibited little or no activity. In addition,performance was generally about 25-50% improved over that shown by theactivated starch:PAM formulations at equivalent doses.

Three-component formulations containing activated starch,starch-maleamate, and PAM were prepared and evaluated, as described inExample 18, employing ratios from 1:1:1 to 10:10:1, preferably 5:5:1 to10:10:1. Again, in the soil vial (static) and soil rill (fluid flow)assays, this formulation performed very well at doses at which thecontrol treatments (no additive, starch-maleamate alone, or PAM alone)exhibited little or no flocculation activity. Performance was generallyabout two-fold improved over that shown by the activated starch:PAMformulations at equivalent doses (i.e. 1 ppm performed at parity to 2ppm activated starch/PAM).

In a useful modification of these formulations, inorganic salts, such asammonium, potassium, calcium, and magnesium salts, can be added toreduce viscosity, thus allowing easier handling of more concentratedformulations. The salts are typically added at a level of 5-10 wt %,depending on the water solubility of the salt. However, levels of 1-50%,more preferably 5-25% or 5-15%, can also be useful. Example 25 providesan illustration of reduction of viscosity by addition of calciumchloride dihydrate or ammonium sulfate to starch/PAM formulations.Preservatives are also recommended to prevent degradation of the starchor microbial growth. Addition of about 6 to 15 ppm of a thiazolone-typepreservative, such as Kathon®, is found to be suitable.

See Section V below for further discussion of these compositions,including performance as soil retention and water infiltration agents.

B. Compositions with Amino Acid Copolymers

Copolymers of aspartate (Asp), asparagine (Asn), and succinimide (Suc),in various combinations, can be used in combination with activatedand/or derivatized starches, as described herein for acrylamidepolymers, to produce flocculating, soil retaining and/or dust controlcompositions. Preferred weight ratios of copolymer to starch are similarto those noted above; e.g. about 1:1 to 100:1 starch/copolymer,preferably about 5:1 to 30:1 starch/copolymer.

Copolymers having a high asparagine content, e.g. about 2:1 to 4:1asparagine/aspartate, are generally preferred. These polymers exhibitgood activity as flocculants and controlled release via furthersolvation over time.

In another embodiment, improved flocculating activity is provided bylightly crosslinking such polymers, as described further below. Finally,water-soluble terpolymers of aspartate, asparagine, and succinimide areparticularly useful for covalent grafting to starch, to produce graftedcompositions that are useful as flocculants. For this purpose, lowmolecular weight polymers are generally preferred.

B1. Preparation of Amino Acid Copolymers

Copolymers of aspartate (Asp), asparagine (Asn), and succinimide (Suc)can be prepared by methods described in Sikes et al. (U.S. Pat. Nos.5,981,691; 6,495,658; 6,825,313). For example, copolymers of aspartateand asparagine can be prepared from polysuccinimide by ring opening withammonia or ammonium hydroxide in water. Polysuccinimides, in turn, canbe produced via routes such as dry thermal polymerization of asparticacid powder, producing molecular weights of 3 to 5 kDa (Example 11).Addition of a phosphoric or polyphosphoric acid produces molecularweights in the range of 30,000 Daltons (Example 2). Molecules as largeas 180,000 Daltons can be produced via an acid solubilization stepcoupled with phosphoric or polyphosphoric catalysis (i.e.; aspartic acidpowder is completely dissolved in water, prior to addition of thepolyphosphoric catalyst, and water is then removed to produce a mixtureready for polymerization). Each of these approaches, along with othermethods for production of polysuccinimide, is detailed in Sikes, U.S.Pat. No. 7,053,170.

Disclosed herein is an improved method for preparing very high MWpolysuccinimides of linear morphology and minimal branching, with MWs upto about 300,000 Da. This approach, as described in Example 3, employstreatment of aspartic acid powder in a soaking step usingphosphoric/polyphosphoric acid with minimal water. Accordingly, asparticacid powder was first soaked in a catalyst-containing aqueous fluid (40%aqueous polyphosphoric acid) that was just sufficient to cover thepowder. This composition was dried at 80° C. overnight in a forced-airoven, then further dried at 120° C. under vacuum prior topolymerization, and then again at 190° C. for 4 hours under vacuum. Thepolysuccinimides so produced are light, off-white materials. Again, MW'sof 180,000 and higher were routinely achieved at 30% catalyst via thismethod. These polymers have minimal or no branching.

Polysuccinimides of defined MW's ranging from 7,000 and higher can alsobe produced via this approach, simply by lowering the catalyst loading.For example, a polysuccinimide of MW 10,000 was so produced at acatalyst concentration of 2%, and MW 15,000 with the catalyst at 3% to4%, by weight of the aspartic powder.

As noted above, copolymers of aspartate and asparagine can be preparedfrom polysuccinimide by ring opening with ammonia or ammonium hydroxidein water.

Alternatively, low MW aspartate/succinimide copolymers may be prepareddirectly, as described by Sikes et al. (U.S. Pat. Nos. 5,981,691 and6,495,658), by thermal condensation of an intimate mixture of ammoniumand sodium aspartate (produced by drying a solution of the two salts,prepared by adding NaOH to ammonium aspartate). Theaspartate/succinimide residue ratio is dependent on the ratio of sodiumaspartate and ammonium aspartate in the original mixture.

As disclosed herein, a useful modification to this process, as describedin Example 4, involves back-titration of an ammonium/sodium aspartatesolution into the pH range of 3-5 prior to drying; this producespolymers having higher succinimide content and better color. In anothermodification disclosed herein, also useful in circumstances where low MWcopolymers are preferred, an anionic counterion is added, which iseffective to block some aspartic amine groups from polymerization. Thismodification is described further in Example 4.

These aspartate/succinimide copolymers can be converted toaspartate/asparagine copolymers by reaction with aqueous ammonia, asdescribed, for example, in Examples 5 and 8a. In another approach,described in Example 9, polysuccinimide is converted directly to anasp/asn copolymer having a high asparagine content (approximately 80 mol% or greater) by reaction with excess ammonia at low temperatures (e.g.2 to 4° C.).

The Asp/Asn copolymers can in turn be converted to water-solubleterpolymers of aspartate, asparagine, and succinimide (see e.g. Examples6 and 8b), by thermal ring closing of some fraction of the asparagineresidues.

B2. Compositions with Polysaccharides

The above-described copolymers and terpolymers of aspartate (Asp),asparagine (Asn), and/or succinimide (Suc) can be used in combinationwith activated and/or derivatized starches, as described herein foracrylamide polymers, to produce flocculating, soil retaining and/or dustcontrol compositions. Preferred weight ratios of copolymer to starch inthese compositions are similar to those noted above; e.g. about 1:1 to100:1 starch/copolymer, preferably about 5:1 to 30:1 starch/copolymer.Terpolymers, particularly those with high asparagine content, are alsoparticularly useful for grafting with starch in preparation offlocculants. These materials can be tested using the assays described inExamples 26-29 for evaluation of these properties. For example, thegrafting of various terpolymers to activated starch, by reaction atbasic pH, is described in Example 13. The product was assessed as aflocculant via the soil-vial assay (Example 26a), exhibiting someinitial activity, with excellent activity developing over a period of 1week. The activity persisted for several months before fading. Theterpolymers with higher mole % asparagine were generally found toproduce the most effective flocculants.

It is found, conversely, that terpolymers having lower mole % asparagineand correspondingly higher mole % aspartate exhibited an increasingtendency towards dispersion activity rather than flocculation activity.Accordingly, dispersion of suspended or emulsified particles, in amixture comprising said particles and water, is promoted by applying to,or including in, said mixture, a composition comprising anaspartate/asparagine/succinimide terpolymer of grafted to starch,wherein the mole % of aspartate residues in the terpolymer is 30% orgreater, preferably 50% or greater.

The grafted terpolymers in both cases are preferably of relatively lowmolecular weight, (prior to grafting); e.g. less than 5000 Da,preferably less than 2000 Da.

IV. Crosslinked Amino Acid Polymers

As described above, copolymers of aspartate, asparagine, and/orsuccinimide can be combined with activated and/or modified starches toproduce flocculating compositions. The flocculating properties ofcopolymers of aspartate and asparagine, preferably having a highasparagine residue content, e.g. >50 mole %, more preferably >75 mole %,are enhanced by lightly crosslinking the copolymers to produce a greatereffective molecular size. A mole ratio of about 80-85:20-15asparagine/aspartate is particularly preferred, with the 15-20 mole %aspartate providing water solubility.

Preferably, the polymers to be crosslinked have a substantially linearmorphology, allowing molecules to have sufficient length to bridge soilparticles in suspension, causing them to flocculate and settle. Lightcrosslinking of such copolymers, as described herein, can be effectiveto increase effective size and thus improve flocculating activity, whilestill maintaining water solubility of the polymers. In this case,although linear starting polymers of high molecular weight (i.e. 100 KDaor more) are preferred, smaller molecules having low to moderate levelsof branching also can be used to build crosslinked flocculants. See, forexample, the data in Table 1 below.

Numerous bifunctional and polyfunctional agents, typically polyols andpolyamines, can be used for crosslinking. Preferred crosslinkers includediamino compounds, such as diaminohexane, ethylenediamine, and lysine,diols, such as 1,2- or 1,3-propanediol, and polyols such as glycerol.Polymeric crosslinkers, such as polylysine, may also be employed.Preferred are diaminoalkanes or alkanediols, having backbones containing2 to 8, preferably 3 to 6, carbon atoms. The diaminoalkane or alkanediolmay be, for example, a 1,2-, 1,3-, 1,4-, 1,5-, or 1,6-diamine or diol.Diamines are particularly preferred; an exemplary crosslinker is1,6-diaminohexane (DAH).

The amount of crosslinker should be enough to produce constructs ofsufficient size and flocculating activity while retainingwater-solubility. Effective molar ratios of monomeric residues in thecopolymer to crosslinker are generally in the range of about 20-35:1 forhigh MW copolymers (e.g. 100 KDa or greater), about 1-30:1 for medium MWcopolymers (e.g. about 10 to 100 KDa), and about 1-10:1 for low MWcopolymers (e.g. less than 10 KDa).

As described in Example 11 below, the crosslinked copolymers may beprepared in a single step from polysuccinimide, via simultaneous ringopening and crosslinking. A low temperature process in which excessammonia is added to the polymer, as described above, is preferred toproduce a high residue ratio of asparagine. Alternatively, preformedaspartate/asparagine copolymers may be reacted with crosslinkers, asdescribed in Example 10 below.

Table 2 includes flocculation data on various crosslinked amino acidpolymers prepared as described herein. Several of the crosslinkedcopolymers exhibited flocculation properties equivalent or superior toPAM, as indicated. In some cases, activity increased over time,presumably via further dissolution of the active agent.

TABLE 1 Summary of Crosslinking Reactions: Copoly(Asp/Asn) materials foruse as flocculants. MW of Expt. starting Mol % Crosslinker Moleratio(s), 1 180,000 48% lysine 10:1 2 180,000 48% dah 10:1 3 180,000 83%dah 10:0.75, 0.625, 0.5, 0.375 4 30,000 50% dah 10:1, 0.75, 0.5, 0.25 530,000 75% dah 10:0.75, 0.625, 0.5, 0.375 6 30,000 83% dah 10:0.4, 0.3,0.2 7 30,000 75% dah/pdiol 10:(0.19 + 0.19) 8 30,000 78% pdiol 10:0.75,0.625, 0.5, 0.375 9 30,000 82% glycerol 10:0.375, 0.25, 0.2, 0.15 1030,000 83% lysine HCl 10:2, 1, 0.7 11 30,000 80% polyLys 10:1 12 30,00080% polyLys 5:, 2:1, 1:1 13 5,000 83% dah 10:1, 0.5 14 5,000 80% lysineHCl 10:2, 1, 0.7 15 5,000 80% polyLys 10:2, 1, 0.7 16 5,000 80% lysineHCl 10:10, 7.5, 5 17 5,000 80% polyLys 10:1 Notes: Experiments 1-12employed the procedure of Example 10; experiments 13-17 employed theprocedure of Example 11. The notation for % Asn refers to the residuemol % of copolymer as Asn via titration data. Crosslinkers used werediaminohexane (dah); lysine HCl (Lys); polylysine (polyLys);1,2-propanediol (pdiol); and glycerol. The polylysine was prepared bythermal treatment of lysine (free base) at 180° C. for 8 hours. Theratio of polymer to crosslinker is given as residue-molesuccinimide:mole of crosslinker molecule for dah, lys, pdiol, andglycerol. For polylysine, the ratio is given on a weight basis.

TABLE 2 Summary of Flocculation Properties for Crosslinked Copolymers ofTable 1. Expt. Flocculation activity (vs. PAM control) 1 No flocculationactivity observed. 2 No initial activity:activity develops after twodays, but < PAM. 3 Partially soluble, better solubility when mortared tofine powder; moderate initial activity, activity increases at 2 h;10:0.5 ratio most effective, ≥PAM. 4 10:0.5 ratio: No initial activity;partially soluble, coarsely ground particles; by 24 hrs approx. = PAM.10:0.75 ratio: Some initial activity, by 24 hrs ≥ PAM. 5 10:0.5 and10:0.375 ratios: Good activity in 15 min., by 2 h, ≥PAM. 6 All samplesmostly soluble, all with good activity; 10:0.3 ratio most active, goodinitial activity, by 24 h ≥ PAM. 7 Some initial activity, improves withtime, but < PAM. 8 Some flocculation activity with time, but < PAM. 9Good activity with time, 10:0.25 ratio best, but < PAM. 10 No initialactivity, moderate activity after 5 days. 11 Partially soluble, someinitial activity, good activity within 7 days, but < PAM. 12 Goodinitial activity, all ≥ PAM within 3 days: 1:1 ratio > 2:1 > 5:1. 1310:0.5 ratio: Mostly soluble, little activity. 10:1 ratio: Partiallysoluble as large solid pieces, some initial activity; when ground tofine particles, improved solubility, good initial activity, comparableto PAM within 2 hours. 14 No initial activity, excellent activity by 6days; 10:2 ratio > 10:1 > 10:7 ≥ PAM. 15 No initial activity, someactivity with time, but < PAM. 16 No initial activity, excellentactivity after 5 days, ≥PAM. 17 Partially soluble, some initialactivity, comparable to PAM by 7 days.

V. Flocculation, Soil Retention, Water Infiltration, and Dust ControlAssays: Exemplary Data

A. Flocculation

Static flocculation properties were evaluated by means of a soil-vialflocculation assay, described in Example 26a; and/or a soil-cuvetteflocculation assay, described in Example 26b. Briefly, in the soil-vialassay, a soil sample is suspended in distilled water, the sample isvortexed, and the test additive composition is pipetted into the vialfrom a stock solution. The suspension is stirred gently, then allowed tosettle for 3 minutes. Settling is visually assessed by observation in alight field alongside control vials with zero additive and/or withspecific amounts of commercial PAM. In the soil-cuvette assay, aliquotsare withdrawn from the suspended samples, and absorbance is measured atintervals at, for example, 400 nm, to determine decrease in lightscattering by the suspended soil particles over time occurred as thefluid clarifies.

The soil-cuvette assay was carried out for soil samples (25 mg in 10 mlwater containing 0.1 M CaCl₂)) containing either no additive, 0.667 ppmPAM (Cytec A110), or the same amount of PAM plus 3.33 ppm activatedstarch. Specifically, the samples designated “PL pr1” through “PL pr3”included the same amount (0.667 ppm) of PAM in combination with 3.33 ppmactivated potato starch. The three PL formulations differed in type ofpreservative: the “pr1” formulation included the preservatives Kathon®(2-octylthiazol-3-one), at a level of 6 ppm of a 4.5% PAM/starchformulation; the “pr2” formulation included the preservative methylparaben, at a level of 0.1 wt % of a 4.5% PAM/starch formulation; andthe “pr3” formulation included the preservative potassium sorbate, alsoat a level of 0.1 wt % of a 4.5% PAM/starch formulation.

This amount of activated starch (i.e. 3.33 ppm) had no significanteffect on settling in this experiment when used alone. As shown in FIG.1, however, its presence significantly improved flocculation activity ofthe combinations relative to PAM alone. (In this experiment, the dataused was part of a set of measurements that had been taken daily over aperiod of a month. Accordingly, the effectiveness of the differentpreservatives had a large impact on the observed results. By the end ofthe month, the paraben- and sorbate-containing formulations haddeveloped microbial contamination; hence, these compositions were lesseffective than the Kathon®-containing formulation. In remainingexperiments, the formulations did not contain preservatives and wereused within days after preparation; contamination was not a factor.) Itwas also observed that the activated polysaccharide was quite effectiveas a flocculant at higher levels, e.g. 10 to 30 ppm (data not shown).

B. Soil Retention

For efficient soil retention, i.e. prevention of erosion, flocculationactivity in itself is required, but, in addition, the flocs or particlesthat form must be stable and dense enough to withstand conditions offluid flow, such as occur during furrow irrigation, or the dynamics ofdroplet impact during spray irrigation.

Flocculation under conditions of fluid flow was evaluated by means of asoil rill assay, employing a lab-scale simulation of furrow irrigation,as described in Example 27. In this assay, water, with and withoutadditives, is pumped down a simulated, sloped soil furrow, and theoutflow is collected in a reservoir. During flow, phenomena such asstability of the soil at the point of inflow, tendency to form channelsalong the rill, stability of the soil along the rill, presence orabsence of floc deposits along the rill, etc., are observed visually.The time until first outflow is recorded, and the amount of soil andwater collected during a predetermined time is determined. The sedimentcould be dried and weighed, or, preferably, the height of the sedimentin the vial was measured as an indicator of erosion (i.e. lack of soilretention).

Effectiveness of soil retention could also be readily ascertained fromvisual inspection of the rill itself, which, when stabilized by aneffective soil-retention agent, exhibited a smooth, somewhat shiny,stable soil surface, with little or no erosion evident. In controltreatments, on the other hand, the flow generated a pattern of erodedmeanders and excavations with an appearance much like an actual flowdown a hillside.

In control experiments, using water with no additives, the collectingvial (20 ml) was typically filled 50% or more (i.e. 10 ml or more) witheroded soil in dark, turbid outflow (see FIG. 8). In an experiment using0.75 ppm PAM (“PAM partial”), an intermediate amount of soil was presentin the outflow (about 4-5 ml depth). Examples of very effectivetreatments included: 3 ppm PAM (“PAM full”); 3 ppm activated starch/PAM(0.5 ppm PAM plus 2.5 ppm activated starch; “SS PL”); and 2 ppmactivated starch-maleamate/PAM (0.33 ppm PAM plus 1.67 activatedstarch-maleamate; “SS PL Plus”). In these cases, the collecting vial wasalmost completely clear of sediment (FIG. 8).

As discussed above, the modified starch compositions alone are goodflocculants in static systems, and provide the benefit of extendedrelease properties, but they are generally less effective underconditions of fluid flow when used alone. However, as shown by theresults above, the addition of these materials to small amounts of PAM(0.33-0.5 ppm) provided clearly superior benefits to larger amounts ofPAM (0.75 ppm) used alone.

C. Water Infiltration

The promotion of uptake of water by soil (water infiltration) wasassessed via two laboratory assays, as described in Examples 28a-b, thenverified via field measurements. In the first, “static” infiltrationassay, infiltration of water into soil samples is measured as the waterpercolates into soil held in vertically placed clear cylinders. Depth ofinfiltration versus time, as well as time of first outflow and totalvolume of outflow, are recorded.

Some representative results that illustrate the improved infiltration ofwater using the present compositions are shown in FIG. 2. The controltreatment consisted of infiltration of soil with tap water. Additivestested included PAM (Cytec A110, 2 ppm) and PAM/activated starchcombinations, where “formula 1” included 2 ppm PAM plus 10 ppm activatedpotato starch (per Example 12a), and “formula 2” included 2 ppm PAM plus10 ppm ColdSwell™ 1111 (KMC) potato starch. In the PAM/starchtreatments, the water infiltrated to significantly greater depthssignificantly faster than did control and PAM treatments. Under theconditions of this laboratory assessment, PAM and the control exhibitedessentially equivalent rates of water infiltration. This observation wasalso made in the field, as described further below.

In the second, “dynamic” assay, infiltration of water into soil wasmeasured as the water was pumped down a rill containing loosely packedsoil. The soil was held in a transparent support so that depth ofinfiltration, as well as lateral infiltration, could be observed. Somerepresentative results are shown in FIGS. 3-5; in these tests, only thecombination agent was employed, along with a control containing noadditive. FIG. 3 shows the increase in lateral advance at a given timepoint for water containing PAM/activated starch (2 ppm PAM plus 10 ppmColdSwell™ 1111 (KMC) potato starch) (“PL”) vs. the control with noadditive. FIG. 4 shows the increase in infiltration depth at a giventime point for the same compositions, and FIG. 5 shows greater depthinfiltration of water for a given amount of lateral advancement for thePAM/starch formulation vs. the control. (Some of the figures suggestthat the control data began to converge with the PL data after about 80cm lateral advance or 8 cm depth. This observation is an artifact of theexperimental setup; at this point, the water had reached the bottom ofthe plastic support in the test apparatus and began to flow quicklyalong the support.)

D. Field Tests: Soil Retention; Water Infiltration

Once a candidate molecule or formulation had shown promising performanceat parity or better to commercial PAM as a flocculent, soil-retentionagent and/or water-infiltration agent, arrangements were made fortesting in actual furrow and spray irrigations on agricultural fields.Test sites were in Idaho and California. Comparisons of experimentalresults were made in side-by-side assessments relative to controltreatments with no additives and with commercial PAM. In furrowirrigation trials, typical flows were purposely set a high levelsranging in general from 5 to 7 gallons per minute and up to 12 gallonsper minute along furrows ranging from 300 to 600 feet, with dosingbetween 1 and 10 ppm of active agents. In spray irrigation, typicalapplications were 2 to 3 pounds of active agents injected into 0.06acre-foot of water per acre (approx 12-18 ppm) using standard irrigationapplication equipment.

The combination agents, containing low doses of PAM plus activatedstarch, performed at parity with conventional applications of PAM in thearea of soil retention. Testing was done using 5:1 activated starch:PAM(designated “PL”) at levels of 6, 12, and 18 ppm, and using PAM at 2 and10 ppm. Some erosion was observed at 6 ppm PL and 2 ppm PAM; none wasobserved at 12 and 18 ppm PL and at 10 ppm PAM.

In contrast to benefits observed in soil retention, the PAM treatmentsalone had little or no effect on water infiltration under the conditionsof the trial. The PL treatments, on the other hand, even at 6 ppm,exhibited marked increases in water infiltration; i.e. a 10 to 20%increase relative to controls (no additives) and PAM treatments. Inpractice, over a typical furrow length (e.g. 500 feet to a′/4 mile),because the improved infiltration effects compound with time, the impactof such a change can be substantial. It was observed that, while theuntreated or PAM-treated water in these tests reached the end of thefield in 2 hours, the PL-treated water (at the same monitored inflowrate) could take 6 hours to go the same distance. This difference couldbe attributed to the PL-treated water infiltrating to a greater depth aswell as going into the soil particles to a greater extent, rather thanflowing around and over them. The difference was seen to diminish as theflow rate was increased to 7.5 to 9 gallons per minute per furrow;however, this rate is considerably greater than used in normal practice(upwards of 4 gallons per minute) for this type of furrow irrigationwhich were set on slopes in the range of 1.5 to 2 degrees.

In view of the above results, the activated starch and modified starchcompositions described herein are recommended for use in improving waterinfiltration, e.g. in irrigation settings, both alone and in combinationwith acrylamide polymers, particularly PAM. As shown for the conditionsabove, levels of 5-15 ppm of the activated and/or modified starches canbe used for this purpose, alone or in combination with 1-3 ppm of PAM.Inclusion of these low doses of PAM clearly provides benefits in soilretention, as shown by the data and results herein.

E. Dust Control

Effectiveness of the compositions described herein for dust control wasevaluated using an assay described in Example 29. Briefly, in a processdesigned to mimic the spraying and drying cycle of a dust control agentsprayed onto a dusty surface, test additives were added to a soil/watermixture (25 mg/2 ml), following by brief mixing, and the mixture wasplaced in a forced air oven at 80° C. until dry. The soil residueadhering to the container surface was covered with water and vortexed,and the turbidity and settling of the resulting fluid were assessed as ameasure of the stabilization of the soil surface by the additive.Effective dust control was evidenced by clear or nearly clear fluidlayers after vortexing, and/or by rapid settling of particles. Controls(with no additive) produced turbid fluids that clarified slowly. PAM,used at a dose of 100 μg, routinely produced turbid fluids, whichclarified quickly, but not as quickly as those produced by theflocculating agents disclosed herein, including activated starch usedalone, maleamate-derivatized starch used alone, and each of thestarch/copolymer formulations described above.

F. Compatibility with Other Agricultural Products

The starch-acrylamide formulations described herein were found to behighly compatible with commonly used commercial fertilizers and withexisting commercial soil penetrant products.

As an example of the former, an exemplary formulation containingactivated starch (Coldswell™ 1111) and PAM (Superfloc® A-110) at 4.5%actives in water (3.75% starch and 0.75% PAM), plus 15 ppmisothiazolinone as a preservative, was formulated, on a 1:1 weightbasis, with commercial fertilizers containing either ammonium nitrateand urea at 32% total actives (16% of each) or ammonium sulfate at 40%actives. The resulting products were evaluated using the vial, cuvette,and rill assays described in Examples 26-27. The performance of thePAM/starch product as a flocculant and soil retention agent wasunaffected by the presence of the fertilizers.

As an example of the latter, the same exemplary starch/PAM formulationwas formulated, on a 1:1 weight basis, with a commercial soil surfactantand wetting agent containing 10% alkoxylated polyol and 7% gluco-ether.The resulting products were evaluated using the vial, cuvette, and rillassays described in Examples 26-27. The performance of the PAM/starchproduct as a flocculant and soil retention agent was unaffected orimproved by the presence of the soil surfactant (which, when used alone,exhibited no activity as a soil retention agent, and acted as adispersant at higher doses, promoting erosion rather than retention).

VI. Clarification of Process Waters from Oil-Sands Mining

Another technology in which improved flocculants are sought is inoil-sands mining and processing. In general, oil-sands deposits consistof sand and bitumen, a semi-solid hydrocarbon material that must beliquefied in order to be transported through a pipeline. Approximatelyeighty percent of the oil-sands deposits in Northern Alberta, Canada aretoo deep to recover by surface mining techniques, and must be recoveredvia wells which are drilled into the deposits. A currently favoredtechnique is steam-assisted gravity drainage (SAGD), in which a largeunderground dome of super-heated steam is formed via steam injectioninto a series of upper wells, liquefying the hydrocarbon material, whichthen flows downwards into wells positioned below the steam-heated dome.The oil is pumped upward to recovery operations at the surface.

In this process, at the surface, roughly three barrels of oily andbituminous-containing water are produced per barrel of oil. This processwater is eventually recycled into the steam generators, but it mustfirst be sent to a processing plant for clarification. The water isinitially at a temperature of 90-95° C. at start of processing; andafter various clarification and purification steps, it may be closer to80° C. before it is recycled to the steam generators. Consequently, theclarification and separation steps need to be effective at 95° C. orhigher, and preferably remain effective for residence times on the orderof several hours or more.

Because of the high oily and bituminous content of the process waters,ranging roughly from 1% to 60% solids, and the elevated temperaturesinvolved, it has been challenging to design effective water-treatmentprotocols that clarify the water and provide good separation of theaqueous and petrochemical phases. Current practice for clarification ofoil-sands process water employs multistep processes using high levels ofparticulate clarifying agents, inorganic salts (e.g. aluminum, iron,magnesium or calcium salts) and/or polycationic agents forde-emulsification and coagulation. Over a period of several hours, aloosely flocculated solid material becomes separated from the water,which can then be recycled to the steam generators. However, this wateroften contains high levels of the additives noted above, and separationof oily solids can still be inadequate.

A significantly improved method and compositions for clarifying suchprocess waters is disclosed herein. This method provides highclarification at surprisingly low doses of active agents, with easilyseparable aqueous and petrochemical phases. Moreover, the separation canbe accomplished in a few minutes, as compared to several hours or morevia current commercial methods.

The invention process preferably includes a first step of neutralizingthe oily, bituminous materials, thus destabilizing the oil-in-wateremulsion. In this step, the pH is adjusted into the range of about 2 to4, preferably about 3 to 3.8, which neutralizes carboxylic-containingorganic phases which would otherwise act as dispersing agents tostabilize the emulsion.

In one embodiment of the process, addition of a polycationic coagulantfollows this pH adjustment. A preferred polycation for this step iscopolymerized epichlorohydrin and dimethyl amine, or poly EPI/DMA.Typically, upon addition of the polycationic coagulant, the oilydroplets are further de-emulsified and tend to slowly coalesce andseparate from the water. With adequate stirring, an interval ofapproximately 30 seconds is sufficient for this step, although longerintervals are effective as well.

Other polycationic coagulants that may be used at this stage includepolymers of cationic monomers such as ammonium alkyl acrylamides (e.g.quaternized dimethylaminopropyl acrylamide), ammonium alkylmethacrylamides (e.g. 3-methacrylamidopropyl trimethylammoniumchloride), ammonium alkyl acrylates (e.g. 2-acrylatoethyltrimethylammonium chloride), ammonium alkyl methacrylates (e.g.quaternized dimethylaminoethyl methacrylate), diallyl dialkylammoniumsalts (e.g. diallyl dimethyl ammonium chloride), allyl trialkyl ammoniumsalts, and amino acids such as lysine or ornithine. The cationic monomeris present at least 50 mole %, preferably at least 70%, and morepreferably at least 80 mole %. In one embodiment, the polymer is ahomopolymer. Other monomers, if present, are neutral monomers such asacrylamide or methyl (meth)acrylate. Examples are homopolymers ofdiallyl dialkylammonium salts or allyl trialkyl ammonium salts.

The molecular weight of the polycationic coagulant is generally at least5000, though higher molecular weights, e.g. 20,000, 50,000, 75,000, orabout 100,000 Daltons, can be used and may be more effective. Themolecular weight of the coagulant is generally less than 1 millionDaltons, and preferably less than 500 kDa.

The amount of polycationic coagulant used is generally in the range of 1to 100 ppm, preferably 5 to 50 ppm or 10-20 ppm. Levels of 2.5, 5, and10 ppm, in combination with similar levels of flocculant (describedbelow) were effective in field tests, as shown in the Examples below. Alevel of 20 ppm, in combination with 40 ppm flocculant, was effectiveeven in downstream wastewaters having about 60% solids (Example 38).This level is clearly substantially less than the several hundred orthousands of ppm of such agents which are commonly used in currentpractice.

The preferred process further employs a flocculant material, which maybe added together with or following the polycationic coagulant, when thelatter is employed. The flocculant is a water-soluble, high molecularweight hydrogen-bonding agent which serves to bridge the droplets andbituminous particulates, flocculate them and bring them quickly out ofsolution or emulsion. Preferred hydrogen-bonding agents are acrylamidecopolymers. The copolymer may be an anionic acrylamide copolymer, suchas an acrylamide/acrylate copolymer (as described above) or, in apreferred embodiment, a cationic acrylamide copolymer (“cationic PAM”),such as an acrylamide/allyl trialkyl ammonium copolymer. Arepresentative cationic acrylamide copolymer is acrylamide/allyltriethyl ammonium chloride (ATAC) copolymer.

These acrylamide copolymers typically have about 50-95 mole %,preferably 70-90 mole %, and more preferably around 80-90 mole %acrylamide residues. The molecular weight of the flocculant copolymersis preferably about 5 to 30 million, more preferably 12 to 25 million,and most preferably 15 to 22 million Daltons. In each case, the mole %acrylamide is at least about 50%, and the molecular weight is at least 1million Daltons, preferably at least 4 million Daltons.

Other cationic monomers that can be copolymerized with acrylamide toform a flocculant copolymer include those noted above, i.e. ammoniumalkyl (meth)acrylamides, ammonium alkyl (meth)acrylates, diallyldialkylammonium salts, and allyl trialkyl ammonium salts. As notedabove, the mole % acrylamide in these flocculants is at least about 50%,and more preferably 80-90%.

The cationic acrylamide copolymers are generally more heat-stable inthese settings than the anionic acrylamide copolymers. At temperaturesabove about 80° C., use of cationic PAM's produces separated flocs thatremain stable for several hours or longer, even at 95° C.

In another preferred embodiment, the acrylamide copolymer is provided incombination with an activated polysaccharide, such as an activatedstarch, as described in Section II above. The ratio of these components(starch:copolymer) is typically in the range of 0.1:1 to 100:1,preferably 0.5:1 to 10:1, more preferably 1:1 to 5:1.

The activated polysaccharide is an extremely high molecular weight,water soluble entity having flocculating activity. Flocculated materialsformed via the action of the PAM/activated polysaccharide compositionstend to be large and very light, having low density. These flocculatedmaterials rapidly form into a robust and integrated floating layer thatis easily skimmed or filtered, leaving behind a greatly clarifiedaqueous layer.

The activated polysaccharide is preferably an activated starch. Asdiscussed in Section II above, activated wheat and coin starches tend toremain active at higher temperatures than activated potato starches, andthus are particularly useful in these high temperature processes.However, as shown in the Examples below, activated potato starch,particularly steam activated, pregelled starch, is also generallyeffective.

Addition of the flocculant composition preferably follows addition ofthe coagulant (e.g. poly EPI/DMA), when present, by an interval of 30-60seconds, or more if desired.

Because the polycationic coagulant tends to interact with anionicflocculants (e.g. acrylamide/acrylate), their effective concentrationwill be lessened with respect to their interaction with the oilybituminous particles. However, these additives may be used together withgood effect if the overall dosing is increased to counteract theirmutual interaction.

The amount of flocculant composition used is generally in the range of 1to 100 ppm, e.g. 2.5-50 or 10-30 ppm. Levels of 30 ppm alone, or 2.5, 5,or 10 ppm in combination with similar levels of a polycationiccoagulant, were effective in field tests, as described in the Examplesbelow. A level of 40 ppm, in combination with 20 ppm coagulant, waseffective even in downstream wastewaters having about 60% solids(Example 38).

The coagulant and flocculant may be used in approximately equal amounts.Alternatively, they may be used in a ratio of up to about 2/1 flocculantto coagulant, or vice versa. Other ratios may also be used as effective.

The entire exemplary sequence (adjusting pH, staging in the coagulant,addition of the flocculant, and skimming/filtration to separate theaqueous layer from the oily/bituminous solids) can generally beaccomplished in a few minutes. The pH of the aqueous layer may then bequickly neutralized via addition of alkali.

Certain steps in this exemplary sequence may be omitted, particularly ifthe others are enhanced accordingly. For example, the pH adjustment maybe omitted (for example, to avoid possible corrosion of mild steelcontainers and pipes) if the dosing of coagulants and/or flocculants isincreased to overcome the dispersancy that is inherent in thenon-neutralized oily/bituminous phase. In practice, it is possible toclarify and separate the aqueous and petrochemical phases in a matter ofa few minutes, employing actives concentrations in the range of 2.5-100ppm, e.g. 10-60 ppm, if the pH adjustment is utilized. If the pHadjustment is not implemented, a combined concentration of actives of100-500 ppm is typically required. However, this higher dosing is stillgenerally much less than used in conventional treatments, and providesimprovements in water clarity, rapidity or response, and ease ofseparation as compared to conventional treatments.

Conversely, the pH adjustment may be included but other steps omitted. Acombination of the pH adjustment with subsequent addition of coagulantalone or flocculent alone can be an effective approach to clarificationof the process water and separation of the aqueous and petrochemicalphases, as shown in the tests summarized in Table 3 below.

It is interesting and useful to note that by varying the relativeamounts of the additive agents, particularly with respect to theactivated polysaccharide, the density of the flocculated solids layermay be adjusted to promote settling of the solids or, as indicatedabove, to produce a floating layer that rapidly rises to the top, whichis often preferable in practice. In current practice, use of inorganiccationic flocculants, such as ferric salts or aluminum salts, tends tomake the solids heavier so that they settle out of the aqueous layer. Inthe processes described herein, use of the polycationic coagulant alonealso produces a solid layer that sinks. However, the flocculantcompositions described herein, containing activated polysaccharides,tend to rapidly produce a low density solids layer which floats on topof a clarified aqueous layer.

In preliminary experiments, samples of process water from oil-sandsmining were obtained for testing, as described in Example 23 below.These samples were dark amber in color, contained significant bitumenparticulates, and had a definite gasoline-like odor. The process waterwas treated with an activated starch/anionic PAM (5:1) formulation, at30 μg/ml, after first rendering the process water mildly acidic. Theparticulates and emulsified petrochemicals rapidly flocculated into aseparate surface layer; the aqueous lower layer, which was much largerthan the surface layer, quickly clarified and within minutes approacheda water-white appearance.

Table 3 below summarizes effects of different parameters of thedescribed processes on clarification of oil-sands process water incontrolled experiments. As shown, addition of activated starch to PAMprovides improved clarification at lower total additive concentration(entries 13-14 and 15 relative to entries 7-8 and 12, respectively). Themost effective treatment employed addition of a polycationic coagulantfollowed by cationic PAM/activated starch (last entry). Further detailsof these experiments, including preparation of flocculant compositions,are provided in Examples 31-38 below.

TABLE 3 Clarification of Oil-Sands Process Waters Total Entry additives,No. Additive ppm pH Result 1 none — not Stable reverse emulsion ofadjusted oily/bituminous phase in process water. 2 none — adjustedProcess water slowly clarifies to 3-3.8 somewhat as small particulatessettle over several hours. 3 poly Epi/DMA ¹ 100-500 not Process waterslowly clarifies as adjusted small particulates settle over 3-6 hours ormore. 4 anionic PAM ² 100-500 not Process water changes quickly overadjusted several minutes into upper, clarifying aqueous layer, solidssettle into lower layer. At temperatures > 80° C., flocs tend todisperse after 30 minutes. 5 cationic PAM ³ 100-500 not Process waterchanges quickly over adjusted several minutes into upper, clarifyingaqueous layer, solids settle into lower layer. At temperatures of 90-95°C., flocs are stable for several hours. 6 poly Epi/DMA  10-100 adjustedProcess water clarifies somewhat as to 3-3.8 small particulates settleover 10 minutes to 1 hour. 7 anionic PAM  10-100 adjusted Process waterforms quickly over to 3-3.8 several minutes into upper, clear, lightyellowish aqueous layer, solids settle into lower layer. Attemperatures > 80° C., flocs tend to disperse after 30 minutes. 8cationic PAM  10-100 adjusted Process water changes quickly over to3-3.8 several minutes into upper, clarifying aqueous layer, solidssettle into lower layer. At temperatures of 90-95° C., flocs are stablefor several hours. 9 poly Epi/DMA 100-500 Not Additives interfere witheach other if and anionic adjusted added together, mixed as one stockPAM, solution. Not as effective as either added together added alone atequivalent doses. 10 poly Epi/DMA 100-500 not Additives work welltogether, and cationic adjusted process water changes quickly into PAM,upper, clarifying aqueous layer, added together more clear thantreatment with additives acting alone; solids stable at 90-95° C.,settle into lower layer. 11 poly Epi/DMA  5-100 adjusted Additivesinterfere with each other, and anionic to 3-3.8 better to addseparately. Process PAM, water clarifies nicely into yellowish, addedtogether clear upper layer; solids settle out, though, not stable attemperatures > 80° C. 12 poly Epi/DMA  5-100 adjusted Additives workwell together, and cationic to 3-3.8 process water changes quickly intoPAM, upper, light yellow layer, more clear added together than treatmentwith additives acting alone; solids stable at 90-95° C., settle intolower layer. 13 anionic PAM 2.5-60  adjusted Excellent separation ofclear, co-formulated to 3-3.8 yellowish aqueous layer and solids withactivated layer within minutes: solids float starch depending on ratioof PAM and activated starch, solids begin to disperse at temperatures >80° C. after 30 minutes. 14 cationic PAM 2.5-60  adjusted Excellentseparation of clear, co-formulated to 3-3.8 yellowish aqueous layer andsolids with activated layer within minutes: solids float starchdepending on ratio of PAM and activated starch, solids stable at 90-95°C. for several hours or more. 15 Poly Epi/DMA 2.5-60  adjusted Excellentseparation of clear, and cationic to 3-3.8 yellowish aqueous layer andsolids PAM layer within minutes: solids float co-formulated depending onratio of PAM and with activated activated starch, solids stable atstarch, 90-95° C. for several hours or more. added together 16 PolyEpi/DMA 2.5-60  adjusted Best separation of all treatments: added first,then to 3-3.8 clear, light yellow aqueous layer and cationic PAM solidslayer within minutes: solids co-formulated float depending on ratio ofPAM and with activated activated starch, solids stable at starch 90-95°C. for several hours or more.

VII. Dry Flocculating Agents

The flocculant compositions described herein can be rendered into driedproducts for later (optional) rehydration and use. This can be done byheating at moderate temperatures to partial dryness. For example, a 2%formulation of activated starch and PAM was treated overnight at 80° C.in a forced-air oven, to produce a material which retained up to 30% aswater, based on weight analysis, but could be handled as a non-sticky“dry” material. The water may also be removed by other methods, such asspray-drying, freeze-drying, or solvent extraction. This dried materialcan be rehydrated at room temperature for preparation of new stocksolutions. Alternatively, the material can be added in this semisolidform to a soil surface, in an amount equivalent to the amount that wouldbe applied in solution, with similar success in stabilizing soil andminimizing erosion under water flow conditions.

It is also possible to blend dry preparations of commercially available,cold-water-soluble starches, such as ColdSwell™ (KMC), with PAM or otherflocculating polymers as described herein, to form a dry product forlater preparation of aqueous compositions for use in soil-retention,water conservation, water clarification, and dust control. Thesestarches are typically prepared as high MW, pre-gelled materials viaaqueous heating using a drum drier, jet cooker plus spray drier, orother commercial heating and drying equipment.

EXAMPLES General Methods

Molecular weight. The molecular weights of the copolymers weredetermined by gel permeation chromatography (GPC) by use of a liquidchromatograph (Agilent 1090) with both diode array (Agilent) andrefractive index (Waters 410) detectors. Gel permeation columnscontained polymer-coated, silica packing (Phenomenex P3000, 4000, 6000columns, plus guard column). Molecular-weight standards were commercialpolyaspartates, copolymers of acrylate and acrylamide, a copolymer ofacrylate and maleate, polyacrylates, dextrans (Sigma-Aldrich) andpolyaspartates prepared in-house. In addition, the molecular weights ofspecific polymers were measured by mass spectroscopy (matrix-assisted,laser desorption (MALDI MS) with time-of-flight detector), and then usedthemselves as standards for GPC determinations.

Color. The color of the copolymers, both as solids and aqueoussolutions, was assessed by visual comparison to color standards (ASTM)available from commercial sources. In addition, the ultraviolet andvisible light spectra of standard aqueous solutions of the copolymerswere compared to indicate the intensity of color development atparticular wavelengths.

Molecular morphology. Branching versus linearity of the copolymers wasassessed in two ways. The first employed an advanced method in atomicforce microscopy. The second utilized quantitative titration of theC-terminal, carboxylic end-groups of polysuccinimide molecules. Thenumber of end groups as compared to the known molecular weight of themolecules can provide an indication of the number of branches, as eachbranch has an end group.

Atomic force microscopy. First, a novel method of atomic forcemicroscopy (AFM) was used to visually inspect the appearance of themolecules at the nanometer and angstrom levels. The method involvedfirst immobilizing the polymers at the surfaces of calcite crystals byallowing the polymers to embed themselves partially at growing crystalsurfaces by placement of functional groups of the copolymers intolattice positions of the crystal surface (Sikes et al., 2000). Thepolymers, so immobilized and held tightly to an atomically flat surface,were then imaged via contact-mode AFM in solution (Digital Instruments,Nanoscope III, Multimode). The visually evident differences betweenbranched versus unbranched molecules were clear.

The AFM was also used to visualize gelled and insoluble particles ofpolymeric materials at the micron and nanometer levels. In the contextof controlled release, this was helpful in correlating dissolution ofparticles over time with the appearance and increase of flocculationactivity.

Infrared spectroscopy. The infrared spectra of copolymers weredetermined by use of an IR spectrophotometer (Perkin Elmer 1600)equipped with attenuated total reflectance. The spectra revealed thecharacteristic amide and imide peaks, thus indicating the presence orabsence of succinimide residues, as well as aspartate, asparagine, andother residues. The spectra also revealed the presence of functionaladditive groups in derivatized copolymers, in particular the glycosidicether linkages of polysaccharides.

Residue ratios via assessment of titratable groups of polymer products.Quantitative acid-base titrations of the copolymers over the pH range of7 to 2.5 were made manually by use of digital pipettors. The procedurebegan with weighing a standard amount of material, typically 100 mg,into a beaker containing distilled water, typically 50 ml. The initialpH was measured and brought to pH 7 by addition of either 1N NaOH or 1NHCl (Fisher Scientific standard reagents and pH buffers). The titrationwas conducted by recording the volumes of titrant (1N HCl) versus pHfrom pH 7 to 2.5. The μmoles of NaOH consumed over this rangecorresponded to the μmoles of titratable groups in the original sample.Controls consisted of titrations of distilled water and standardcompounds including reagent grade aspartic acid, purified sodiumpolyaspartates, purified polyaspartic acids, purified polysuccinimides,and purified polyasparagine (Sigma Chemical). The amount of acid or basethat was consumed over this range indicated the amount of titratablegroups of aspartic acid per unit weight of the copolymers.

The material was then back-titrated to pH 7 using 1N NaOH, as acomparison and check on the downward titration, then continued to pH10.0. The solution was warmed to 60 to 65° C. to facilitate the mild,alkaline ring-opening of succinimide residues, if any. Amounts of 1NNaOH were added to maintain the pH at 10.0 until the downward pH driftthat accompanies the ring-opening (as OH⁻ molecules are consumed)ceased. This volume also was recorded as an indication of the amount ofsuccinimide residues that had been converted to aspartate residues.

As a more quantitative measurement of the appearance of new aspartateresidues in the solution, the downward pH titration was repeated. The pHwas adjusted to pH 7 via additions of 1N HCl. The titration was thencontinued to pH 2.5, again recording the volume of titrant versus pH.The number of μmoles of succinimide residues in a particular polymerproduct was determined from the difference between the μmoles of HClneeded to titrate from pH 7 to 2.5 after the ring-opening procedure, ascompared to the original amount of μmoles of HCl consumed from pH 7 to2.5 by the initial polymer material.

The number of micromoles of aspartate residues and succinimide residueswas next converted to an amount in milligrams. The difference betweenthe original amount of sample and the amount of aspartate andsuccinimide residues corresponded to the amount of nontitratable mass inthe original sample. For the terpolymers of aspartate, asparagine, andsuccinimide, the mass of nontitratable materials is equivalent to theamount of asparagine residues. In cases in which extra mass of titrantor additives were present in the dried bulk polymer samples, appropriatecorrections were made.

Amino acid analysis. The copolymers were hydrolyzed via acid treatmentto produce the monomeric constituents. These were then treated to formtheir phenylthio carbamyl derivatives by use of phenylisothiocyanate.The derivatized amino acids were next separated via reverse-phase,liquid chromatography and identified by comparison to chromatograms ofstandards of the amino acids, also so treated. This method generatedquantitative data of the amino-acid composition of the copolymers.

Examples 1-3 Preparation of Polysuccinimide Starting Materials Example 1Preparation of a Low MW (3 to 5 kDa) Moderately Branched PolysuccinimideVia Dry Thermal Polycondensation of Aspartic Acid

An amount of 1.0 mole of aspartic acid (133 g, Solutia) spread evenly ina pyrex dish (2.5×10×15 inches) was thermally polymerized in a vacuumoven (30 in Hg) at 220° C. for 4 hours. The resulting polysuccinimide,which was obtained in essentially quantitative yield of 97 g, had amolecular weight of 5 kDa as shown by gel permeation (weight average).It was moderately branched as shown by titration of carboxylate groups,indicating a branch point at roughly 1 in 10 residues. The color of thesolid product was light tan. The IR spectrum showed a characteristicimide peak at 1705 cm⁻¹ and an amide signal at 1524 cm⁻¹, indicative ofring-opened residues, as would occur at branch points. (2949 w, 1705 s,1524 w, 1390 m, 1359 m, 1287 w, 1258 w, 1212 m, 1162 m)

Example 2 Preparation of Medium MW (Approximately 30 kDa MolecularWeight) Unbranched Polysuccinimide Via Phosphoric or PolyphosphoricAcid-Catalyzed Thermal Polycondensation of Aspartic Acid

A mixture of 1.0 mole of aspartic acid (133 g; Sigma-Aldrich) and 40 gpolyphosphoric acid (i.e. about 30% by weight of the aspartic acid) wasprepared by weighing the polyphosphoric acid onto the aspartic powder ina large pyrex dish. (Phosphoric acid can be used to replace thepolyphosphoric acid partially or entirely at this step, essentially atthe same weight percent. Polyphosphoric acid, although more expensive,tends to result in products of somewhat larger molecular size and better(lighter) color, and is more effective as a dehydration agent.)

Upon heating at 150° C. for 15 minutes in a forced-air oven, followed bymanual stirring with a spatula, and repeating this procedure 3 times, atranslucent, homogeneous paste of the catalyst and aspartic acid wasproduced. This mixture was then polymerized by heating in a vacuum ovenat 190° C. for 4 hours. The polymerizing mass tends to rise as the waterof condensation is evolved, beginning particularly as the temperaturereaches 160° C. To collapse the mass and keep the product more dense,the vacuum was released periodically over the first interval of up to 1hour. After this, the mass was stable and the vacuum was set atapproximately 30 inches of Hg.

The product was converted to fine granules by suspending in water andpulverizing in a blender. The mixture was filtered and the productwashed thoroughly with water until the pH of the wash water was greaterthan 6.0. There was essentially no residual phosphate in the product asshown by spectrophotometric analysis, using the molybdate assay forphosphate. The polysuccinimide product, obtained in nearly quantitativeyield, was light cream in color, insoluble in water, and had agel-permeation (weight average) molecular weight of approximately 30kDa. The titration data for carboxylic groups indicated the presence offew branch points (less than 1 per 10 residues), as also shown by a lackof the amide peak at 1520 cm⁻¹ in the IR spectrum, as would occur if theamide bonds of branch points were present. (IR 3622, 2946, 1704, 1390,1369, 1297, 1258, 1210, 1159, 633 cm⁻¹).

An infrared spectrum of sodium polyaspartate prepared from thispolysuccinimide showed the diagnostic amide doublet in the region of1500-1600 cm⁻¹, and carboxylate signals, sharply at 1395 cm⁻¹, andbroadly in the region of 3200 to 3300 cm⁻¹ (IR 3278 s, 1582 s, 1520 s,1395 s, 1316 w).

Example 3 Preparation of Unbranched Polysuccinimides Having MWs up to300 kDa, Via Phosphoric and/or Polyphosphoric Acid Saturation ofAspartic Acid Prior to Thermal Polycondensation

As carried out conventionally, phosphoric and/or polyphosphoriccatalysis of thermal condensation of aspartic acid to producepolysuccinimide typically results in products in a range up to 30 kDa.Sikes (2004, US Appn. Pubn. No. 2004/0072984) taught the production ofpolysuccinimides in the MW range up to 180,000 and higher via an acidsolubilization step during which the aspartic acid powder was completelydissolved in water prior to addition of the polyphosphoric acidcatalyst. A composition ready for polymerization was then produced bydrying or otherwise removing the water. The method took advantage of theutility of intimately and maximally mixing the polyphosphoric catalystwith the aspartic powder. It has been found that still larger moleculescan be produced via the further modification described below.

An amount of 4 g of polyphosphoric acid was weighed into a 250 ml pyrexdish. To this was added just enough water, approximately 5 ml, to cover13.3 g of aspartic acid powder with no visible layer of water above thelevel of the aspartic powder (as previously determined). The water pluspolyphosphoric acid was stirred for 15 minutes to ensure complete mixingof the catalyst with the water. The 13.3 g of aspartic acid powder wasthen gently poured into the center of the dish and evenly spread overthe bottom of the dish by gently tapping the dish on the surface of thebench. This slurry of aspartic acid powder, catalyst, and water wasallowed to soak for 1 hour, then placed in a forced-air oven to dryovernight at 80° C. This resulted in a dried mass of aspartic acidcrystals that were evenly coated with polyphosphoric acid catalyst.

The dish was then placed in a vacuum oven and the aspartic acidpolymerized at 190° C. under vacuum for 4 hours. The resulting productswere polysuccinimides of molecular weights ranging up to 300 kDa, asshown in Table 4.

The polysuccinimides so produced are light, off-white materials. Again,MW's of 180,000 and higher were routinely achieved at 30% catalyst viathis method. These polymers have minimal or no branching.

Polysuccinimides of defined MW's ranging from 7,000 and higher were alsoproduced via this approach simply by lowering the catalyst loading. Forexample, polysuccinimides of MW 10 KDa and 15 KDa were produced atcatalyst concentrations of 2% and 3-4% by weight, respectively, ofaspartic acid.

For comparison, in some experiments, the amount of water in the disheswas tripled, leaving a clear layer of water above the powder. On drying,this resulted not only in a concentration of the catalyst in a film onthe glass surface rather than associated with the aspartic crystalsthemselves, but also in lower MW of the product polysuccinimides.

TABLE 4 Production of polysuccinimides via thermal condensation ofaspartic acid presoaked in polyphosphoric acid catalyst. Molecularweight of the product polysuccinimide, kDa Minimal water required tocover aspartic acid powder used: % polyphosphoric acid by weight ofaspartic acid 0 5 1 8 2 10.5 3 14.5 10 20.5 15 23 20 30 25 160 30 193 40282 Excess water used: % polyphosphoric acid by weight of aspartic acid4 13.6 5 12 30 28

Examples 4-8 Production of Oligomeric Copolymers of Aspartate,Asparagine, and Succinimide Example 4 Production of Very Low MW,Branched Copolymers of Sodium Aspartate and Succinimide, ViaBack-Titration of Comonomer Preparation, Followed by ThermalPolycondensation

A sample of 19.95 g of aspartic acid (0.15 mole, MW=133 g/mol,equivalent to 0.3 moles of COOH groups) was weighed into a 2-literbeaker containing 100 ml of water with smooth magnetic stirring. To thismixture (pH 3.1) was added 3.75 ml of 10 N NaOH (37.5 mmol) withstirring, raising the pH to 5.0. Residual crystals remained undissolved.Next were added 7.7 ml of concentrated NH₄OH (14.8 M, 0.88 g/ml; 114mmol) with stirring, raising the pH to about 7.5. (Because of its highvapor pressure, aqueous ammonia does not pipette well, making itpreferable to weigh in the required amount.)

To this mixture was added 1.05 ml concentrated H₂SO₄ (36 N, 37.5 meq)with stirring, lowering the pH to about 4.7.

The resulting solution was dried overnight at 120° C., yielding ayellowish glass mixed with some whitish, clear crystals, presumablyinorganic sulfates. This comonomeric composition was polymerized at 220°C. for 4 h under vacuum. The product (17.34 g) was light cream-coloredto yellowish, much lighter in color than comparable material prepared asabove but without the back titration with sulfuric acid. The product waswater soluble at 100 mg/50 ml, pH=5.79.

Titration indicated 95 μmol NaAsp (13.11 mg) per 100 mg (16.7%, residuebasis: 22% weight basis), 475 μmol succinimide residues (46.07 mg) per100 mg (83.3% residue basis: 77.8% weight basis). This amounted to atotal of 59.8 mg per 100 mg accounted for via titration. Thenontitratable weight is assignable to inorganic salt (Na₂SO₄) and toresidues that form aspartyl branch points, which are not titratable.

Example 5 Conversion of the Sodium Aspartate/Succinimide Copolymer ofExample 4 to a Copolymer of Sodium/Ammonium Aspartate and Asparagine, byRing Opening with Ammonium Hydroxide

A sample of 15 g of the copoly(NaAsp, Suc) produced in Example 4 wasplaced in 250 ml water in 500 ml poly bottle. To this was added 25 mlconcentrated NH₄OH, the bottle capped firmly, then swirled manually,with dissolution in about 5 minutes. The bottle warmed mildly to thetouch. The material was poured into a large pyrex dish and driedovernight at 60° C. with forced-air. The yield was 18.206 g. Based ontitration of aspartate groups and change in mass, it was estimated thatabout 60% of succinimide residues were converted to asparagine and about40% to ammonium aspartate.

Example 6 Conversion of Copoly (Aspartate/Asparagine) of Example 5 toTerpoly(Aspartate/Asparagine/Succinimide)

The copolymer of Example 5 (18.1 g) was dissolved in 100 ml water in a2-liter beaker, forming a complete solution. The initial pH was 5.61.The solution was titrated to pH 4.0 by addition of 1.85 ml (22.38 mmol)of 12.1 N HCl. This solution was dried overnight at 60° C. in aforced-air oven, then converted to the terpolymer via ring-closing at170° C. for 3 h under vacuum with rotation of the position of the samplein the oven at 1.5 h. The product (16.232 g) was light amber in color;if temperatures higher than 180° C. were used, the sample tended todarken significantly. The material was mostly soluble at 100 mg/ml,producing a medium yellowish solution, with some insoluble flakes. Basedon titration and weight change, residue mole percentages were estimatedto be 25% aspartate, 32% asparagine, and 43% succinimide.

Example 7 Production of Very Low MW, Branched Aspartate/SuccinimideCopolymers Via an Anion-Blocking Method of Comonomer Preparation,Followed by Thermal Polycondensation

A sample of 13.3 g of aspartic acid (0.1 mole, MW=133 g/mol, 200 m(μ)molof COOH groups) was placed in a 250-ml beaker containing 40 ml of water.Initial pH was 2.99. To this mixture was added 6.75 ml of concentratedNH₄OH (100 mmol) and 3.46 g of MgSO₄ (12.5 mmol Mg²⁺, equivalent to 25mmol of cationic charge, and 25 mmol of anionic charge). Upon drying,this is expected to produce about 75 mmol of Asp as the ammonium salt,which would convert to succinimide upon heating, and 25 mmol as the Mgsalt, the other 25 mmol of ammonia having vented to the atmosphere.There would be 25 mmol of aspartate residues having SO₄ ²⁻ ascounterions to the cationic amino groups of the residues. The Mg²⁺ ionsupon drying, if occurring as ionic counterions to form salts with theCOO⁻ groups, would block these groups from thermal condensation reactionto form the polymer as reported in the prior art. Analogously, but novelto the present invention, the SO₄ ²⁻ ions upon drying, if occurring asionic counterions to form salts with the NH₄ ⁺ groups, would block thesefrom reaction during the thermal polymerization step. Hence, thecomonomeric composition was dried overnight at 120° C., producing apale, yellowish glass, then polymerized at 220° C. for 4 h in a vacuumoven, with rotation of the beaker at 2 hours. The product was a pale,cream-colored powder, expected to have a residue ratio of about 1:3aspartate:succinimide. Titration revealed residue percentages of 27% asMg aspartate and 73% as succinimide (1:2.7 residue ratio). The molecularweight as shown by gel permeation was approximately 1000 Daltons. Thematerial was partially water soluble, having an initial pH of 4.14.

The procedure was repeated using 2.05 g of MgSO₄ heptahydrate (8.33 mmolMg²⁺ and SO₄ ²⁻, equivalent to 16.7 mmol each of cations and anions).Upon drying, this is expected to produce about 83.3 mmol of Asp as theammonium aspartate, with 16.7 mmol as Mg aspartate. In this case, thetarget upon polymerization was a copolymer of aspartate and succinimidewith a 1:5 residue ratio. The product had a residue ratio of about 20%Mg aspartate and 80% succinimide (1:4) and was largely insoluble. Themolecular weight as shown by gel permeation was approximately 1500Daltons.

Repeating the procedure with addition of higher amounts of MgSO₄, totarget residue ratios in the range of 1:1 to 1:2, were successful inproducing the desired copolymers of aspartate and succinimide. In thesecases, the copolymers were water soluble, again having molecular weightsin the oligomeric range (600 to 1000 Daltons).

Example 8a Conversion of the Aspartate/Succinimide Copolymers of Example7 to Aspartate/Asparagine Copolymers, by Ring Opening with NH₄OH

Samples of 5 g each of the first and secondcopoly(aspartate/succinimide) copolymers of Example 7 (ratios of 1:2.7and 1:4, respectively) were placed in 50 ml H₂O in 500 ml wide-mouthplastic bottles. To effect ring opening, these samples were treated withexcess NH₄OH (10 ml of 14.8 M solution), and the solutions were pouredinto 250 ml pyrex dishes and dried at 80° C. (maximum temperature)overnight in a forced-air oven.

Example 8b Further Conversion to Aspartate/Asparagine/SuccinimideTerpolymers

The products of Example 8a were dissolved in 50 ml water in a smallbeaker, and the solutions were titrated to pH 4 via addition of H₂SO₄,transferred to small pyrex dishes, redried at 80° C., and finallyconverted to the terpolymers via ring-closure at 170° C. for 3 hoursunder vacuum. Titration revealed aspartate:asparagine:succinimideresidue percentages of 28:53:19 for the first terpolymer and 22:60:18for the second.

Examples 9-11 Production of Flocculant Materials of CrosslinkedCopoly(Aspartate/Asparagine) Example 9 Production ofAspartate/Asparagine Copolymers Having High Asparagine Content fromPolysuccinimides (Examples 1-3)

A sample of 97 g (1 residue mole) of the polysuccinimide of Example 1(MW 5,000) was slurried in 500 ml water in a plastic bottle and treatedwith 3 eq NH₄OH. The polysuccinimides of Examples 2 and 3 (MW's 30,000and 180,000 respectively) were treated similarly, with longer timesrequired for reaction and dissolution. The solutions were poured intolarge pyrex dishes and dried at 80° C. overnight in a forced-air oven.This procedure was found to produce a maximum asparagine content ofabout 60 mol %.

By repeating the procedure with the NH₄OH addition step carried out atlow temperatures, e.g. 2-4° C., higher asparagine content could beattained. In these experiments, the slurried polysuccinimide and theconcentrated NH₄OH were precooled prior to mixing. The amount ofpolysuccinimide was reduced to 0.1 residue mole (9.7 g) and the amountof ammonium hydroxide was also reduced tenfold, to 0.3 moles.

In further experiments, the temperature was lowered to −12° C., or to−20° C., at which point the aqueous ammonia slurry tended to freeze. Thereactions were allowed to proceed until the polysuccinimide was fullysolubilized, typically within 2 hours. In cases in which the reactionmixture was frozen, the reaction was allowed to proceed for up to 18hours without full dissolution of the reaction mixture. However, thematerial was fully soluble upon warming to room temperature.

In all cases, the low-temperature treatments generated higher asparaginecontent in the copolymer products. With 3-fold excess or higher ofammonia relative to succinimide, at −10 to 2° C. with vigorous stirring,copolymers with >83 mole % asparagine residues were produced, theremainder being ammonium aspartate residues.

Example 10 Production of Flocculant Materials Via Thermal Crosslinkingof the Copoly(Aspartate/Asparagine) Polymers of Example 9

Samples of 500 mg of the aspartate/asparagine copolymers of Example 9were weighed into 100-ml beakers and dissolved in 10 ml water withmagnetic stirring. Crosslinkers were added in various amounts togenerate residue-to-crosslinker ratios of various amounts; for example,9:1, 8:1, 7:1, 6:1, 5:1, and 4:1. Typically ratios were on a molar basisalthough in some instances weight ratios were used. Examples ofcopolymers and crosslinkers are given in Table 1 above.

The mixtures were dried overnight at 80° C., then heated at 170° C. for3 h under vacuum. Products were weighed and assessed for solubility andflocculation activity, via the soil assays described in Examples 26-27.Results are summarized in Table 2, above.

Example 11 Production of Flocculant Materials Via SimultaneousNucleophilic Ring-Opening and Crosslinking of Polysuccinimides

The reaction conditions and procedures of Example 9, for production ofcopolymers of ammonium aspartate and asparagine from polysuccinimides,were followed with the additional inclusion of crosslinker moleculesalong with the ammonium hydroxide. Accordingly, a sample ofpolysuccinimide, preferably comprised of high MW, linear molecules (e.g.from Example 3), was slurried in water at 20 g in 100 ml water. Theslurry was cooled to 2-4° C., by use of a refrigerated recirculatingbath and a water-jacketed glass vessel, and precooled, concentratedammonium hydroxide (twofold excess) was added, keeping the temperatureat 2-4° C. The crosslinker, in a cooled solution of ammonium hydroxide,was added to the precooled slurry of polysuccinimide, and the reactionmixture was then stirred for 2 to 4 hours until a complete solution wasformed. Water was removed at 80° C. in a forced-air oven, producing adried product of lightly crosslinked aspartate/asparagine copolymer.

Example 12a Activation of Starch Via Aqueous Thermal Treatment inSuspension

1. A sample of 10 g of potato starch (KMC) was slurried in 500 ml ofwater at room temperature in a 2-liter beaker, itself placed in a waterbath. Stirring was provided from above via rheostated motor fit with aspatula. The apparatus was placed on a thermostated hotplate and thetemperature raised to 75° C. with continuous monitoring via digitalthermistor. As the temperature increased to 60° C., the material beganto gel, and upon reaching 70-75° C., it became more translucent. Thetemperature was held at 75° C. for 1 hour, then quickly reduced to <60°C. by pouring the sample into a large pyrex dish, then allowed togradually cool further to room temperature. The sample is stable oncecooled to <60° C. 2. To assess the activity of the material as aflocculant, soil-vial and soil-cuvette assays (see Examples 26a and 26b,below) were run over the concentration range of 5 to 300 μg/ml. Theactivated starch was an excellent flocculant in these assays at 30μg/ml, with measurable activity at 10 μg/ml, decreasing to controllevels at 5 μg/ml. 3. Activated starch by itself, although performingwell in static assays, did not function well as a soil-retention agentunder the dynamic flow conditions of the soil-rill assay. Although thesoil particles are formed into large flocs in the presence of activatedstarch, these flocs are less dense and loosely held together as comparedto flocs formed in the presence of copolymers of aspartate/asparagine oracrylate/acrylamide. 4. Potato starch became deactivated by heating inwater at temperatures above 85° C. for 1 hour. If so treated at 80° C.,it began to lose flocculation activity after 2 hours of heating. Aqueousheat treatment at 70 to 75° C. for 1 to 2 hours was optimal with themild stirring conditions as described in step 1 above. With vigorousstirring, as may be provided in commercial equipment such as theLittleford reactor (example 25), activation may occur more quickly, forexample in 15 to 30 minutes at 70° C. 5. A variety of other starchesfrom several suppliers were also activated as flocculants via aqueousheat treatment. Corn starch and wheat starch required heating in therange of 90−95° C. to become activated, but were deactivated if suchheat treatment were extended much over 1 hour. 6. The starches were heatactivated at concentrations up to 10% by weight, although concentrationsbelow about 5% were preferred, due to lower viscosity and relative easeof stirring. 7. The flocculation activity of the activated starches inthe soil-vial assay increased remarkably with time. The initial activityof an activated starch at 30 μg/ml was roughly equivalent to that of PAMat 10 μg/ml. However, after a few days during which the soil suspensionplus additive was incubated on the bench, the activated starch, even atthe lower doses, was outperforming 10 μg/ml of PAM. This activity oftenpersisted for several months before beginning to fade. 8. On the otherhand, the activated starches were not as effective as PAM assoil-retention agents in the soil-rill assay (Example 27 below).Although the activated starches were able to stabilize the soil in therill assays at the top near the inflow, they were not able to stabilizethe soil for the entire length of the minifurrow.

Example 12b Activation of Starch by Jet Cooking; Formulations ofStarch-Based Flocculants and PAM

It is also useful to activate starch and/or starch/PAM combinations viarapid heating methods, e.g. using steam for brief intervals.

Accordingly, slurries of 3.75% by weight each of potato starch, wheatstarch, and corn starch, in amounts of about 40 gallons, were preparedin tap water at room temperature. To each was added 0.75% by weightcopoly(acrylate, acrylamide) (Cytec A-110 PAM) by smooth and continuousaddition over about 30 seconds, with sufficient stirring to quicklydisperse the PAM before it began to swell and agglomerate. Stirring wascontinued for 1 hour or more to allow dissolution of the PAM.

Each starch/PAM preparation was pumped into the reaction chamber of ajet-cooker at approximately 2 liters per minute, with steam set togenerate a chamber temperature of 84 to 110° C., depending on the typeof starch used. In experiments with potato starch, the jet-cooktemperature was 84-88° C., with 84° C. preferred under the conditionsused. In experiments with wheat or corn starch, the jet-cook temperaturewas 100-110° C., again with the lower temperature preferred under thespecified conditions. The residence time in the chamber wasapproximately 2 to 3 minutes. Temperature in the reaction chamber wasrecorded continuously by thermistor.

Pumping was continuous into and through the reaction chamber, withoutflow first to a heat-exchange loop and then into a product reservoir.The product was quickly cooled to 45° C. upon exit from the reactionchamber. Preservatives typically were stirred into the products uponcooling. The temperature in the reservoir was also monitored via digitalthermistor thermometer.

The activity of the products as flocculants and soil retention agentswere demonstrated by use of the soil-vial, soil-cuvette, and soil-rillassays, described in Examples 26-27 below.

Example 13 Improvement of Starch as a Flocculant by Grafting ofAspartate/Asparagine/Succinimide/Terpolymers

1. A sample of 100 mg of potato starch was slurried in 10 ml of water ina 100 ml beaker with smooth magnetic stirring, then heat-activated at70° C. for 1 hour. At a residue weight of 162 mg per mmol, this formed acolloidal solution with an equivalence of 61.5 mmol of glucose residues.2. A sample of 200 mg of the very low MW NaAsp/Asn/Suc terpolymer ofExample 8b was dissolved in 50 ml water in another 100 ml beaker. Thisterpolymer had a residue composition per 100 mg of 170:408:190 (22:53:25residue-mole %) Asp:Asn:Suc residue-μmol per 100 mg. 3. The terpolymersolution was added to the starch colloidal solution with stirring. 4.The mixed solution of starch and the terpolymer was adjusted to pH 11.3via addition of 10 N NaOH by digital microliter pipette. 5. Thenucleophilic ring-opening was allowed to proceed for 30 minutes, thenthe solution was neutralized to pH 7 with 1 N HCl. At this point, thematerial had been rendered completely soluble. 6. The sample wasassessed as a flocculant via the soil-vial assay (Example 26a),exhibiting some initial activity, with excellent activity developingover a period of 1 week. The activity persisted for several monthsbefore fading. 7. A variety of other terpolymers were grafted to starchvia this method. The most effective grafted materials utilized the verylow MW terpolymers having the highest res-% as asparagine. The larger MWterpolymers were not as readily grafted to starch. 8. The terpolymerswith lower res-% as asparagine and correspondingly higher res-% asaspartate exhibited an increasing tendency towards dispersion activityrather than flocculation activity. That is, the soil particles in thesoil-vial assay tended to remain as a cloudy suspension rather thansettling quickly as compared to control vials with no additives.

Example 14 Improvement of Starch as a Flocculant by NucleophilicDerivatization with Maleamic Acid Via Michael Reaction

1. Potato starch was slurried as 200 mg starch in 10 ml water withsmooth magnetic stirring in a 30 ml capped glass bottle placed on astirplate in a forced-air oven at 70° C. for 2 hours. Given a residueweight of glucose of 162 mg/mmol, there are approximately 1.23 mmol asglucose in 200 mg starch. 2. The pH was adjusted to approximately 12.5by addition of 10 N NaOH. 3. Next, an equivalent amount of sodiummaleamate was added. The sodium maleamate had been prepared from 142 mgof maleamic acid (MW 115.09, 1.23 mmol, Aldrich Chemical) plus 3.77 mlof water and 1.23 ml of 1 N NaOH (1.23 mmol). 4. The pH was adjusteddownward with 0.2 to 0.4 ml of 1 N HCl to approximately pH 12,equivalent to 0.01 N NaOH. 5. The reaction was allowed to proceed for upto 3 hours at 70° C., with formation of O-linked starch-maleamate graftsvia nucleophilic addition of OH groups of starch across the double bondof sodium maleamate. 6. Controls of both starch and maleamate were alsotreated as above for later analysis to insure that they did not degradeunder the reaction conditions. Gel permeation and infrared analysisshowed that the materials are stable for 3 hours under the statedconditions. 7. The samples were cooled to room temperature by placementof the bottles in an ice bath. The materials were then neutralized to pH7 using 1 N HCl. 8. The maleamate-derivatized starch(“starch-maleamate”) was assessed for flocculation activity by use ofthe soil-vial and soil-rill assays. The materials were excellentflocculants under the static conditions of the soil-vial assay, withincreasing activity over the range of 5, 10, and 30 μg of graftedmaterial per ml of soil suspension. 9. The flocculation activity in thesoil-vial assay increased remarkably with time. The initial activity ofthe modified starch at 30 μg/ml was roughly equivalent to that of PAM at10 μm/ml. However, after a few days during which the soil suspensionplus additive was incubated on the bench, the modified starch, even atthe low doses, was outperforming PAM at 10 μg/ml. This activitypersisted for several months before beginning to fade. 10. On the otherhand, like the activated, underivatized starch, the maleamate-modifiedstarch was not as effective as PAM in soil-retention, as assessed viathe soil-rill assay (Example 27). In this case, however, although thematerials tended to perform poorly at the inflow of the rill, they wereable to stabilize the soil toward the end of the rill (where each run ofthe rill was less than 10 minutes in duration).

Example 15 Starch-Maleate Dispersants Produced Via Nucleophilic Reactionof Maleic Anhydride or Maleic Acid with Starch

The reaction conditions of example 14 were followed, substituting maleicanhydride or maleic acid for maleamic acid. The grafted compositions soproduced exhibited marked dispersive activity rather than flocculationactivity. That is, when assessed via the soil-vial assays, the soilparticles in the presence of starch-maleic grafts (starch-maleatematerials) settled much more slowly than occurred in control treatmentswith no additives.

It was also possible to simultaneously graft both maleamic acid andmaleic acid to starch. This produced compositions having attenuateddispersive or flocculation activity, depending on the relative amountsof maleamate- or maleate-substituted glucose residues in the resultantstarch-grafted compositions.

Examples 16-17 Formulations of Copolymers, Activated Starch, andStarch-Maleamate as Flocculants and Soil Retention Agents Example 16Formulation of Activated Starch and PAM

1. Potato starch was activated as exemplified above at 75° C. for 1hour, using a 5% by weight suspension in tap water. 2. A commercialsample of PAM (Cytec Superfloc A-836, MW ^(˜)18 million, ^(˜)82 res-%acrylamide) was dissolved in tap water at 1% by weight. 3. A 1:1composition of these components was prepared by mixing equal volumes ofthe activated starch and PAM preparations, giving a weight ratio of 2.5%activated starch to 0.5% of PAM, designated as a 10:2 (or 5:1)preparation. 4. A variety of other mixtures were similarly prepared, atratios ranging from 10:0.5 to 10:5 activated starch:PAM. 5. Theseformulations were assessed for flocculation activity via the soil-vial,soil-cuvette, and soil-rill assays (Examples 26-27). In addition, fieldassessments in both furrow-irrigation and spray irrigation (Example 30)were run in some cases. 6. Results for the synergistic formulations ofactivated starch and PAM were compared to control treatments with noadditive, with activated starch alone, and PAM alone. 7. In each of theassays in the cases above, including conditions of turbulent flow of thesoil-rill assay, the synergistic formulations performed very well atdoses at which the activated starch alone or the PAM alone exhibitedlittle or no activity. In the field work, in general, the synergisticformulation of activated starch and PAM at ratios of 10:1 and higherperformed at parity to PAM at equivalent doses, even though the actualdose of PAM was up to ten-fold lower in the synergistic formulation. 8.Activated starch was also formulated with PAM over a range of otherdoses and ratios up to 100 ppm and 30:1. Flocculation activity in thevarious assays was good at doses of 5 to 30 ppm, using ratios up to 30:1of activated starch:PAM. 9. It was also possible to activate the starchin the presence of pre-solubilized PAM by forming a slurry of the starchin the dissolved PAM at lower temperature (less than 50 to 55° C.), thento raise the temperature for heat activation of the starch as above. 10.Similarly, it was possible to first form a suspension/slurry of starchfollowed by rapid introduction of undissolved PAM with vigorous stirringat lower temperatures, followed by stirring of the mixture sufficientlyfor long enough to dissolve the PAM, still keeping the temperature belowthe gelling point of the starch. In this preferred method of premixingthe components, it is necessary that the PAM is well dispersed in thefluid over an interval of about 30 seconds. This allows the PAMparticles to become dispersed before the viscosity of the fluidincreases too much as the PAM dissolves. The PAM particles then dissolvewith further stirring and processing of the starch/PAM formulation. Ifthese conditions of vigorous stirring and rapid dispersion are notpresent, the PAM particles begin to solubilize at their surfaces, whichbecome sticky, quickly adhere to one another and to dispersed starchparticles as well, and form into essentially insoluble largeragglomerations that are not further processable.

Next, the temperature was raised to heat-activate the starch. In eitherarrangement of this example (steps 9 and 10), the activated starch-PAMformulations exhibited significant synergism as flocculants andsoil-retention agents. However, reiterating, one should ensure that thePAM is dissolved, or at least well dispersed, prior to heat treatmentfor activation of the starch, to avoid the formation of gelledagglomerations of undissolved PAM particles and starch particles, singlyor in combination. Both PAM particles and starch particles tend to formsuch relatively insoluble, partially gelled clumps when heated too fastwith insufficient stirring.

Example 17 Formulation of Maleamate-Modified Starch and PAM

1. The maleamate-modified starch of Example 14 was formulated withcommercial PAM by mixing separate stock solutions. Typical ratios of theactive agents ranged from 10:0.5 to 10:5 of maleamate-modified starch toPAM. 2. These formulations were assessed for flocculation activity viathe soil-vial and soil-rill assays (Examples 26-27). 3. Results forthese synergistic formulations of starch-maleamate and PAM were comparedto control treatments with no additive, with starch-maleamate alone, andwith PAM alone. 4. In each of the assays in the cases above, includingthe conditions of turbulent flow of the soil-rill assay (to assess soilretention), this formulation performed very well at doses at which thecontrol treatments exhibited little or no flocculation activity.Moreover, this formulation exhibited a fractional improvement (i.e. 25to 50%) relative to the activated starch:PAM formulation at equivalentdoses.

Example 18 Formulations of Activated Starch, Starch-Maleamate, and PAMas Soil-Retention Agents

1. The activated starch of Example 12a and the starch-maleamate ofExample 14 were formulated with commercial PAM by mixing separate stocksolutions. Typical ratios of the active agents as activatedstarch:starch-maleamate:PAM ranged from 5:5:1 to 10:10:1. 2. Theseformulations were assessed for flocculation activity via the soil-vialand soil-rill assays (Examples 26-27). 3. Results for these 3-part,synergistic formulations of activated starch, starch-maleamate, and PAMwere compared to control treatments with no additive, with activatedstarch alone, with starch-maleamate alone, with a mixture of activatedstarch and starch-maleamate, and with PAM alone. 4. In each of theassays in the cases above, including the conditions of turbulent flow ofthe soil-rill assay (to assess soil retention), the 3-part synergisticformulations performed very well at doses at which the controltreatments exhibited little or no flocculation activity. Moreover, the3-part formulation at actives ratios in the range of 5:5:1 to 10:10:1 ofactivated starch, starch-maleamate, and PAM in general exhibited atwo-fold improvement in performance relative to the activated starch:PAMsynergistic formulation at an equivalent dose (that is, for example, ata 3-part dose of 1 ppm performed at parity to a 2-part dose at 2 ppm).

Example 19 Formulations of Activated Starch, PAM, and Starch-Maleamateas Water-Infiltration Agents

Representative materials of Examples 15, 16, and 17 were evaluated aswater-infiltration agents by use of the static and dynamic infiltrationassays (Examples 28a-b), and also in field assessments. These materialsclearly promoted water infiltration in each of these assessments, withincreases in the range of 10 to 20% relative to rates of infiltration incontrol treatments. As discussed above, PAM alone showed little or noeffect on water infiltration in these tests.

Example 20 Preparation of the Above Formulations as Dried Products

Samples of 50 ml of a 2% formulation of activated starch and PAM (5:1)were treated overnight and over periods of several days in 250 ml dishesat temperatures ranging from 60 to 120° C. in a forced-air oven. About80° C. was found to be an optimal temperature; lower temperaturesproduced insufficient drying, and materials dried at higher temperatures(>90° C.) were sometimes difficult to reconstitute. The material driedat 80° C. retained up to 30% as water, based on the weight analysis, butit could be handled as a non-sticky “dry” material, and it could berehydrated at room temperature for preparation of new stock solutions,or added “dry” in the assays. For example, to run a rill-assay (Example27), it was possible to simply sprinkle an amount at the point of inflowequivalent to the amount that would be applied in solution, then to flowtap water down the rill, generally with equivalent success instabilizing the soil and minimizing the erosion.

Materials may also be dried via other methods, such as spray-drying,freeze-drying, or solvent extraction.

Example 21 Other Dry Formulations of Starch-Based Flocculants

It is also possible to blend dry preparations of commercially available,cold-water-soluble starches with PAM as a dry product for laterpreparation of aqueous stocks of the synergistic formulations for use insoil-retention, water-conservation, water-clarification, anddust-control. The so-called, water-soluble starches are typicallyprepared as pre-gelled materials via aqueous heating using a drum drier,jet cooker plus spray drier, or other commercial heating and dryingequipment. If the starches so-produced retain sufficient molecular size,when dissolved with PAM, or provided as a separate aqueous stocksolution with aqueous PAM, a formulation that functions well insoil-retention, water-conservation, water-clarification, anddust-control is produced. Such formulations were assessed via thesoil-retention, water-clarification, and water-infiltration methods ofthe present invention, including field assessments. The preferredformulations from the dry blends of starch and PAM performed at paritywith the formulations of Examples 15 through 18.

Example 22 Utility of Starch-Based Flocculants and OtherPolysaccharide-Containing Materials as Dust-Control Agents

Each of the flocculants and soil-retention agents of the presentinvention as detailed above were assessed as potential dust-controlagents via the dust-control assay. Each of these materials andformulations of theses materials performed better than PAM in this assayincluding activated starch on its own, starch-maleamate grafts on theirown, and each of the starch-based formulations as indicated in the aboveexamples. In addition, a number of commercial polysaccharides performedvery well in this assay, exhibiting marked improvements relative to PAMalone in direct comparisons on an equivalent weight basis. Examples ofsuch polysaccharides, obtained from commercial suppliers (Fluka,Sigma-Aldrich), included agar, carrageenan, chitosan, carboxymethylcellulose, guar gum, hydroxyethyl cellulose, gum Arabic, pectin, andxanthan gum.

Example 23 Utility of Starch-Based Flocculants and OtherPolysaccharide-Containing Materials in Treatment of Process WatersGenerated in Mining Operations

In mining of oil-sands, large volumes of hydrocarbon- andbitumen-enriched process water are generated that must be clarified andpurified prior to re-use or return to the environment. The compositionsof the present invention exhibited excellent utility in this regard. Forexample, process water from oil-sand mining operations was obtained andtreated with an activated-starch/PAM formulation at 30 μg/ml. Theprocess water in its untreated state is a darkly-colored amber, containssignificant bitumen particulates, and has a definite gasoline-like odor.Within seconds following treatment with the composition of the presentinvention, the particulates and emulsified petrochemicals form intolarge flocs in a surface layer. These can be easily separated from thelower water layer by skimming. The aqueous lower layer, which is muchlarger than the surface layer, quickly clarifies and within minutesapproaches a water-white appearance.

Treatment with the flocculating agents can be enhanced by concomitantadjustment of the process water to 0.1 to 3 mM acid, to lower the pH inthe range of pH 3. Inclusion of inorganic salts such as aluminum orferric sulfate, at a final dilution of about 0.1 to 3 mM, along with thecompounds of the present invention and the low pH treatment, provides anadditional benefit in clarifying the process water. If desired, anyresidual color in the water layer can be further clarified via additionof small amounts of activated carbon.

For further examples of this utility, see Examples 31-38 below.

Example 24 Preservation and Stability of the Starch-Based Flocculants,Polyamino Acid Flocculants, and Biopolymer-Based Dust-Control Agents

Samples of the starch-containing formulations, if prepared with cleanvessels and nonsterile tap water, were stable for 1 to 2 weeks at roomtemperature, but often began to exhibit biological contamination afterthat. Light microscopic examination revealed the presence of bothbacteria and fungi, and often both, in various samples as timeprogressed.

It was possible to prevent microbial growth in the aqueous formulationsof the samples for up to several months at room temperature by additionof commercial preservatives, such as benzoates, sorbates, andisothiazolinones, at doses recommended by commercial suppliers of theseagents (e.g., in the range of 0.1% to 0.6% by product weight for thebenzoates and sorbates, and 6 to 15 ppm for the isothiazolinones). Insome cases, for example with addition of potassium sorbate to theaqueous product formulations, the viscosity of the starch-based productswas noticeably lessened, improving the ease of handling and metering ofthe products in agricultural applications. The isothiazolinones weregenerally the most effective as preservatives.

In addition, it is useful to keep the samples sealed to the atmosphereprior to use, to minimize the interaction of oxygen with the flocculantmolecules and formulations.

Example 25 Lowered Viscosity and Increased % Solids of FlocculantFormulations Via Addition of Inorganic Salts

In the absence of viscosity modifiers, the % solids of the starch/PAMflocculant materials are limited in a practical sense, due to the highviscosity of the formulations at 5 wt % or higher. It is possible todecrease the viscosity, thereby enabling use of higher % solids of theflocculant formulations, by addition of inorganic salts such as calciumchloride and ammonium sulfate, among others. The inorganic salts mayalso be added to the make-up water before addition of the starch andPAM, which are then heat-activated.

To illustrate this effect, a formulation of 15 liters of activatedpotato starch and PAM in a weight ratio of 3.75% starch:0.75% PAM (5:1)was prepared. The starch was first slurried in tap water, followed byrapid addition of the PAM with concurrent vortexing. This starch/PAMpremix was then poured a water-jacketed, 20-liter Littleford reactor.Heat was provided to the reactor via a recirculating bath set to 90° C.to produce an internal target temperature reached 70-73° C., which washeld at this range for about one hour.

The internal temperature was then lowered below 40° C. within minutes bycirculation of cool tap water to the water jacket. Preservatives wereadded, and the flocculant composition was transferred into a 5-galloncarboy. Subsamples of this material were then taken for viscositymeasurements.

Inorganic salts added at various doses to selected subsamples were shownto reduce viscosity. For example, addition of 5 g of CaCl₂) dihydrate to80 g of a 4.5% starch/PAM formulation reduced the observed Brookfieldviscosity at 100 rpm from 750 to about 500 centipoise, a reduction ofapproximately 33%. The addition of calcium, or other multivalentcations, may also result in increased flocculation activity.

In a further experiment, increasing amounts of ammonium sulfate wereadded to the in the make-up water in the preparation of activatedstarch/PAM products. The effect on viscosity is shown in FIG. 6.

At 15% by weight (NH₄)₂SO₄, the constituents of the sample formulationsprecipitated with time; that is, within a week, about the upper ⅓ of thevolume of the samples became substantially clarified as a hazysupernatant layer. This effect was also observed to some extent in thesamples containing 5% by weight (NH₄)₂SO₄.

At 50% by weight (NH₄)₂SO₄, the formulation is prepared as an opaqueemulsion; however, within a few minutes, the activated starch and PAM(of the PL 4.5% formulation) precipitated almost in their entirety;hence the very low viscosity, approaching that of water.

Although these low-viscosity formulations are suspensions and slurriesrather than solutions, they have utility nonetheless in providing anaqueous preparation of starch/PAM formulations of relatively high %actives. These preparations can be stirred, poured, and pumped and donot contain the insoluble, bulky, partially gelled particles thattypically occur when mixing and/or heating relatively highconcentrations of PAM and starch without the additives as describedherein.

The compositions of the samples and observed viscosities at 100 rpm, incentipoise, are as follows. “PL 4.5%” refers to a composition ofactivated potato starch and PAM in a weight ratio of 3.75% starch:0.75%PAM, as described above.

A) PL 4.5% 1158 B) PL 4.5%, 5% (NH₄)₂SO₄, 553 C) PL 4.5%, 10% (NH₄)₂SO₄,503 D) PL 4.5%, 15% (NH₄)₂SO₄, 370 E) PL 4.5%, 20% (NH₄)₂SO₄, 275 F) PL4.5%, 25% (NH₄)₂SO₄, 170 G) PL 4.5%, 50% (NH₄)₂SO₄, 4 H) PL 7.5%, 15%(NH₄)₂SO₄, 642 I) PL 10.0%, 15% (NH₄)₂SO₄. 984 J) PL 7.5% 2500

Examples 26-28 Soil-Flocculation and Soil-Retention Assays

Soil was obtained from the US Department of Agriculture, AgricultureResearch Service from a test site in Idaho so that lab assessmentsmatched a soil type later encountered in some of the field trials. Inaddition soil was assessed from a number of sites in the Californiavalleys and from several sites around Eugene, Oreg. Soil types wereselected to encompass sandy, clay-enriched, and organic enriched soils,as well as soil types that were intermediate in their composition.

Example 26a Soil-Vial Assay

The soil-vial flocculation assay involved suspension of a soil sample indistilled water in the presence or absence of the additives at differentdoses. The water contained divalent cations at 0.1 molar (calcium and/ormagnesium) because the cationic content has been shown as a significantvariable in flocculation activity (Dontsova and Norton, 2001). Ingeneral, at least some cationic content is useful in promotingflocculation.

Although a variety of arrangements are possible, routine measurementsinvolved a soil sample of 25 mg placed in 10 ml of 0.1 M CaCl₂) in a 20ml vial. The soil-vial was then vortexed (Vortex Genie 2, VWRScientific) at high speed for 10 seconds to standardize the initialparticle distribution and turbidity. The experimental polymer sample wasthen pipetted into the vial from a stock solution. A typical effectivedose of additive was 10 μg/ml (ppm), with dosing often ranged from 1 to300 μg/ml. The soil suspension was stirred gently by manually fillingand draining a 3-ml bulb pipettor (Fisher Scientific) twice, thenallowed to settle for 3 minutes.

For visual assessment of settling, the soil suspension was gentlyswirled manually then placed in a light field for inspection of settlingof particles and clarification of the supernatant. This permitted arapid assessment of flocculation activity (soil suspensions in the vialsclarify quickly) or dispersion activity (soil suspensions in the vialsclarify slowly) as compared to control vials with zero additive or withspecific amounts of commercial PAM. In the case of PAM-treatedsoil-vials or treatments with promising experimental flocculants, theresults are obvious in a matter of seconds even via such visualinspection.

Example 26b Soil-Cuvette Assay

To quantify flocculation activity in the soil-vial assay, 2 mlsubsamples of soil plus fluid as prepared above were taken from thevials by digital pipettor. Next, the 2 ml samples of the soil suspensionwere gently pipetted into a polystyrene cuvette with 1 cm path length(Brandtech UV). Absorbance at 400 nm (other wavelengths can also beused) was recorded quickly at 3 seconds then at 10 second intervals overa total of 180 seconds via the kinetics program of a spectrophotometer(Spectronic Genesys 5). Decrease in light scattering by the suspendedsoil particles versus time occurred as the fluid clarified. Higher ratesand total amount of decrease corresponded to increased flocculationactivity accompanied by more rapid clarification of the fluid.Representative results from use of the soil-cuvette assay, forformulations containing PAM and/or activated starch, are shown in FIG. 1and described in Section V.A above.

Example 27 Soil-Rill Assay

The soil-vial and soil-cuvette assays, above, are helpful for detectingflocculation activity under the static conditions that occur after theinitial swirling or pipetting of the samples. In the case ofsoil-retention agents, flocculation activity in itself is required, butin addition the flocs or particles that form must be stable enough anddense enough to withstand conditions of fluid flow such as occur duringfurrow irrigation and the dynamics of droplet impact during sprayirrigation.

To further assess the potential utility of candidate soil-retentionagents, a lab-scale simulation of furrow irrigation was used. To dothis, devices termed minifurrows (soil plus holder) were constructed foruse on the bench top. Once the minifurrow was set on a slope andprovided with a fluid flow, the construct was termed a soil rill(minifurrow plus small stream).

The lab minifurrows were constructed in 6-feet lengths of polyethylenehalf-cylinders that were attached to strips of wooden molding via Velcroadhesive tapes. The polyethylene furrows were cut from pipe insulationobtained from local building suppliers. At the outflow end, apolyethylene spout to promote smooth and uniform outflow was cut from aplastic weighing dish and inserted into a slit cut into the terminaledge of the minifurrow.

Preparation and placement of the soil. Soil (typically 1 to 5 kg) wasspread into large pyrex dish(es) and dried at 90° C. overnight. The soilwas next ground through 20 mesh using a Wiley mill to standardized theparticle size. Then, 200 g samples of the soil were sealed in plasticbags to minimize uptake of moisture from the air. This was useful inlowering variability of erosion measurements.

To prepare a minifurrow, samples of 200 g of the soil were spread evenlyover the length of a minifurrow, leaving an uncovered space ofapproximately 1 inch at the outflow end. This small zone provided aspace useful for newly-forming flocs of soil particles to settle.Otherwise, these nascent flocs, owing to a lack of time and region forsettling, would flow directly into the collection vial, obscuringresults. Next a piece of ¾ inch PVC pipe was laid in the furrow andgently rolled by hand to form the soil into a homogenous layer having ashallow concave surface to promote direct flow of the fluid down thecenter of the furrow.

The minifurrow was then placed in a holder constructed of foam-coreboard to provide a defined slope. In experiments, the slopes were setbetween 2 and 30 degrees, with 10 degrees used in most of themeasurements. By comparison, slopes on actual fields range from about 2degrees to very little slope at all, sometimes adjusted to a fractionaldegree via laser-leveling technology. Hence, the elevated slope in thesoil-rill assay was selected to provide a rigorous test of candidatesoil-retention agents.

The soil rill. With the minifurrow so prepared and set on an incline,the final step was to introduce a flow. Water (local tap water) wasprovided to the minifurrow through Silichem™ tubing set in a holder atthe top so that the flow began dropwise at the upper center of thepacked soil. The water was pumped at varying rates, typically 20ml/minute for the 10 degree incline, via a peristaltic pump (ColeParmer). A set volume of water, usually 250 to 300 ml in a beaker, withand without additives was provided as the reservoir for each experiment.

As the water ran down the minifurrow, observations were made visuallysuch as stability of the soil at the point of inflow, tendency to formchannels along the rill, stability of the soil along the rill, presenceor absence of floc deposits along the rill, and the like. A 20-ml vialwith funnel was placed below the outflow spout and the first 20 ml ofoutflow were collected. The duration of an erosion experiment of thistype typically ranged from 8 to 10 minutes. The time until first outflowwas recorded for each experiment. Representative results are describedin Section V.B above. The apparatus is illustrated in FIG. 7.

Examples 28a-b Water Infiltration Assays

The agents of the present invention are novel not only in theircomposition and performance in soil-retention but also in their abilityto promote uptake of water by the soil. This property was assessed viatwo laboratory assays, then verified via field measurements.

The first laboratory assay involves measurement of infiltration of waterinto soil samples under essentially static conditions as the waterpercolates into soil that was placed in clear, acrylic cylinders. Thismethod is termed the static infiltration assay.

The second laboratory assay is designed to measure infiltration of waterunder more dynamic conditions of fluid flow, as the water was pumpeddown clear, acrylic rills containing loosely packed soil. This method istermed the infiltration plexirill.

Example 28a Static Infiltration Assay

Clear acrylic tubing of 1 inch inner diameter was obtained from a localsupplier and cut into segments ranging from 1 to 3 feet. Soil samples ofvarious types, ranging from local soils to soils obtained atexperimental sites in Idaho and California, were dried at 90° C. Samplesof these in amounts of 200 g were then poured using a funnel into thecylinders. The bottoms of the cylinders were sealed with filter paperand tape to keep the soil in while allowing air and water to flow out.

A reservoir for infiltration of water and additives was prepared inadvance by adding 65 ml of tap water plus 5 g of the soil used to formthe column in the cylinder. The soil was gently slurried into the watervia smooth magnetic stirring. Candidate additives were next dosed intothe water-plus-soil suspension via pipetting from stock solutions toyield a treatment in the range of 10 μg/ml. The additives were thusadded as a component of a flocced soil preparation, mimicking thecarriage of soil particles along a furrow by the fluid phase.

The water-plus-soil preparations were pipetted onto the surface of thesoil in increments of 5 ml at a rate sufficient to maintain a fluidlayer of 10 mm. A total of 60 ml of fluid was introduced to the uppersurface of soil in the cylinder in this manner. Movement of the waterinto the column of soil was followed visually, while recording depth ofinfiltration versus time as well as time of first outflow and totalvolume of outflow.

Some representative results that illustrate the improved infiltration ofwater using the compositions of the present invention are shown above inFIG. 2 and described in Section V.C. A schematic of the apparatus isshown in FIG. 9.

Example 28b Dynamic Infiltration Assay

A transparent “minifurrow” was constructed from clear acrylic materials.The dimensions were 6 feet in length, 6 inches in height, and 1-inchinner width. The acrylic sheets used to construct the device were ¼ inchthick and very high transparency. The ends were configured to slide upand down to allow outflow at the lower end of the rill, and also forease of emptying the wet soil from the apparatus at the end of anexperiment.

To set up an experiment, 8 kilograms of dried soil were added to theplexirill by use of a funnel. A furrow was set into the surface bypressing a ½ inch dowel into the soil. The furrow was placed in a holderto provide an incline at 10 degrees. A peristaltic pump (Cole Parmer)was used to provide a flow to the top of the furrow at a rate of 75ml/minute from a 2-gallon reservoir. Markings were drawn onto one sideof the plexirill to indicate the lateral spacing at 10-cm increments anddepth in 1 cm increments to a total depth of 15 cm.

During an experiment, measurements at minimum were recorded versus timeas the flow passed each lateral mark of 10 cm and the depth ofinfiltration at that point. Typically the timing of other points ofinfiltration according to the characteristics of a particular treatmentwere recorded as well. Other data included the time and total amount offluid applied to the furrow prior to first outflow, and also the rate ofoutflow at intervals until such time that the rate of inflow and rate ofoutflow equalized.

Differences in infiltration between rills treated with effectiveinfiltration agents and control treatments having no additives wereeasily observed via these measurements. Some representative comparisonsare shown in FIGS. 3-5 and discussed in Section V.C above. A drawing ofthe apparatus is shown in FIG. 10.

Example 29 Dust-Control Assay

This assay also involved a suspension of a soil sample in 0.1 M CaCl₂ inthe presence or absence of additives at different doses. In this case,routine measurements involved a soil sample of 25 mg placed in 2 ml of0.1 M CaCl₂ in a 20 ml vial, enough fluid to cover the soil completely.The experimental polymer sample was then pipetted into the vial from astock solution in amounts ranging from a total of 10 micrograms to 3milligrams. The soil suspension was stirred gently by swirling manually.The vial was then uncapped and placed in a forced-air oven at 80° C.overnight for complete drying. This procedure mimicked the spraying anddrying cycle of a dust control agent sprayed onto a dusty surface. Upondrying, the soil, now adhering to the glass surface, was covered with 10ml of 0.1 M CaCl₂ or tap water. The vial was next vortexed for 5 secondsat high speed, then turbidity of the fluid and settling of the soilparticles were assessed as a measure of the stabilization of the soilsurface by the additive. Results were compared to those for controltreatment with no additives and with PAM.

An effective dust-control additive stabilized the soil very well underthese conditions, resulting in clear or nearly clear fluid layers aftervortexing. If there were turbid layers in the treated samples aftervortexing, the fluids became clarified by settling of the soil particleswithin seconds. By comparison, the no-additive controls had turbidfluids that clarified slowly. The PAM-alone treatments, at a dose of 100μg, routinely produced turbid fluids that clarified quickly but moreslowly than those of effective dust control additives.

Example 30 Field Experiments in Agricultural Settings

Once a candidate molecule or formulation had shown promising performanceat parity or better to commercial PAM as a flocculant and soil-erosionagent, and in a number of instances as an water-infiltration agent,arrangements were made for testing in actual furrow and sprayirrigations on agricultural fields. Test sites were in Idaho andCalifornia. Comparisons of experimental results were made inside-by-side assessments relative to control treatments with noadditives and with commercial PAM. In furrow irrigation, typical flowsranged in general from 5 to 7 gallons per minute and up to 12 gallonsper minute. Furrows typically ranged from 300 to 600 feet, but were upto ¼ mile in length in some cases. Dosing typically was between 1 and 30ppm of active agents. In spray irrigation, typical applications were 2to 3 pounds of active agents injected into 0.06 acre-foot of water peracre using standard irrigation application equipment. Results arediscussed in Section V.D above.

Examples 31-38 Clarification of Process Waters from Oil-Sands MiningExample 31 Preparation of Exemplary Anionic Flocculant Formula

The formula was prepared at 1.4% actives by weight in water (i.e. 14 gpolymer per 1000 g), plus 15 ppm preservative, as follows.

A 1% aqueous wheat starch formulation was prepared by adding 10 g ofwheat starch (MGP Midsol, a native wheat starch from Midwest GrainProducts) to 986 g of distilled water. The starch formulation washeat-activated at 95° C. for 1.5 h with stirring; the temperature wasmonitored and the slurry/emulsion kept from boiling and scalding. Aviscous, partially solubilized, partly nanophased aqueous preparation ofactivated starch was produced. After cooling the mixture, the weightlost as vapor during heating was restored by addition of water.

To this preparation was added 4 g of anionic PAM (80:20acrylamide/acrylate copolymer; Floerger AN 923 VHM; MW approx. 15million Da) to give a ratio of 5:2 activated starch:PAM. The PAM wasstirred in quickly over an interval of 30 seconds followed by vigorousmixing by use of a hand-held mixer for 10 to 15 minutes. The preparationwas allowed to further dissolve with smooth magnetic stirring overnight.A preservative (1 ml of a 1.5% commercial isothiazolinone preservative)was also added.

Example 32 Small Scale Assays of High Temperature Oil-Sands ProcessWater Clarification Using Anionic Flocculant Formula

The stock solution prepared in Example 31 (14 mg actives/g) was dilutedby combining 1 g with 13 g water, resulting in a secondary stocksolution of 1 mg actives per g.

Glass vials containing 10 ml of oil-sands process water, obtained froman oil-sands plant in Canada, were preheated to 95° C. in a forced airoven. To these samples were added up to 80 μl of 1N H₃PO₄ as needed tobring the pH to ^(˜)3.0. (Other acids that were tried, e.g. HCl, HNO₃,H₂SO₄, yielded the same overall results.) The amount of acid requiredfor this adjustment varies, depending on the % solids andcharacteristics of the experimental water. The beneficial effect oflowering the pH is even more marked at lower values, in the range of pH2.0 to 3.0, but values above about pH 3.8 proved less effective.

To each vial was added 300 μg of secondary stock solution, to give adose of 30 ppm actives. The vials were swirled gently, and the contentswere then allowed to coagulate for ^(˜)1 min. The vials were againswirled gently, to allow the agglomeration to form and rise.

The lower aqueous phase was seen to be clear and substantially lighterin color. The upper solids phase floated rapidly to the surface uponsubsequent stirring.

Performance of the product was also assessed in combination withpolyEpi/DMA (for example, Floerger FL 3249 or Baker Petrolite BPW 76355)over a range of concentrations of 10 to 100 ppm actives. However, due tointeraction between the positive and negatively charged formulations,the performance of the starch/PAM flocculant formula alone was superiorin these tests to an equivalent total amount of the starch/PAMflocculent formula plus polyEpi/DMA.

Example 33 Preparation of Exemplary Cationic Flocculant Formula

The formula was prepared at 1.4% actives by weight in water (i.e. 14 gpolymer per 1000 g), plus 15 ppm preservative, as follows.

A sample of 1000 g formula containing 7 g Coldswell™ 1111, aspray-cooked (pregelled) potato starch provided by KMC (Denmark), in 986g of distilled water was prepared by quickly stirring in the starch,with continued vigorous stirring for 10 to 15 minutes. Moderate stirringwas continued for 1 hour.

To this mixture was added 7 g of cationic PAM (80:20 acrylamide/allylethyl triammonium chloride copolymer; Flopam PO 4290 SH; MW approx. 8million Da) to give a ratio of 1:1 activated starch:PAM. The PAM wasmixed in within 30 seconds with vigorous stirring so that it dispersedwell before swelling and clumping. Mixing was continued for 10 to 15minutes with a hand-held mixer. A preservative was added to a finaldilution of 15 ppm (1 ml of 1.5% isothiazolinone per 1000 ml of sample).

Example 34 Small Scale Assays of High Temperature Oil-Sands ProcessWater Clarification Using Cationic Flocculant Formula

As described in Example 32, above, a secondary stock at 1/14 dilutionwas prepared by combining 1 g of the 1.4% cationic flocculant (Example33) with 13 g water.

Vials containing 10 ml of oil-sands process water were preheated to 95°C. in a forced-air oven. To each vial was added up to 80 μl of 1 NH₃PO₄to bring the pH to ^(˜)3.0. To each vial was then added 300 μg ofsecondary stock solution, to give a dose of 30 ppm actives. The contentswere swirled gently, then allowed to flocculate for 1 min. The vialswere again swirled gently, to allow the agglomerates to form and rise.

Within a few minutes, the fluids within the vials were substantiallyclarified, with a clear, lower aqueous layer and a buoyant, floatinglayer of solids of flocked oily/bituminous material.

Example 35 Small Scale Assays of High Temperature Oil-Sands ProcessWater Clarification Using Cationic Flocculant Formula (Example 33) inCombination with a Polycationic Coagulant

Performance of the cationic PAM/starch flocculant of Example 33 was alsoassessed in combination with polyEPI/DMA (for example, Floerger FL 3249or Baker Petrolite BPW 76355) over a range of concentrations of 10 to100 ppm actives, either separately or at the same time with thecationic, hydrogen-bonding flocculant.

When added separately, the poly Epi/DMA was pipetted into the vialcontaining the oil-sands process water at a range of doses. The vialswere swirled for intervals of 10, 20, 30 seconds and higher. Then thecationic PAM/starch flocculant was added, and the vials were swirledagain.

When the poly Epi/DMA treatment was carried out for 30 seconds or moreunder the conditions tested, then the subsequent addition of thecationic PAM/starch flocculant resulted in the most clarity of the fluidphase observed in the experiments described thus far. In addition, thesolids layer was very buoyant, rising quickly to the surface withinseconds, in the form of a few large agglomerates. These results wereobserved at a total dose, for example, of 30 ppm, consisting of 10 ppmpoly Epi/DMA and 20 ppm cationic PAM/starch flocculant.

Example 36 Field Tests of High Temperature Oil-Sands Process WaterClarification Using Anionic Flocculant Formula (Example 31)

A sample of 400 ml of freshly collected process water from an oil-sandsprocessing plant was measured into a flask. The temperature of the waterwas about 90-95° C.

To the water sample was added 1.28 ml of 2N HCl to adjust the pH to^(˜)3.6, as measured by combination electrode. The fluid was swirledmanually for a few seconds to allow the anionic phase of theoily/bituminous materials to become neutralized.

After approximately 30-60 seconds, 6 ml of a secondary stock solution (2mg/ml) of the anionic PAM/starch flocculant formula (Example 31) wereadded. This amount is equivalent to 12 mg actives in 400 ml, which is 30mg/liter (30 μg/ml), or 30 ppm.

The fluid was swirled manually for a few seconds to promote mixing andthe formation of self-adhering flocs. The sample was then allowed tosit. Within a few minutes, the solution became substantially clear, witha lower layer of flocced oily/bituminous solids.

Example 37 Field Tests of High Temperature Oil-Sands Process WaterClarification Using Cationic Flocculant Formula (Example 33) inCombination with a Polycationic Coagulant

Several samples of 400 ml of freshly collected process water from anoil-sands processing plant was measured into respective flasks. Thetemperature of the water was about 90-95° C.

To each water sample was added 1.28 ml of 2N HCl to adjust the pH to^(˜)3.6 to 3.8. The fluid was swirled manually for about 30 seconds toallow the anionic phase of the oily/bituminous particles to becomeneutralized.

To each sample was then added an aliquot of poly Epi/DMA from a 5 mg/mlstock solution sufficient to provide a predetermined dose of 1.25 to 30ppm actives. The samples were then swirled for about 30 seconds, toallow the polycation to adhere to the particulates and tackify them

To each flask was then added an aliquot of cationic starch/PAMformulation (Example 33) sufficient to provide a predetermined dose of1.25 to 30 ppm, or a total of 2.5 to 60 ppm total actives.

The fluid was swirled manually for about 30 seconds to promote mixingand the formation of self-adhering flocs. The samples were then allowedto sit.

Within a few minutes, the solutions became very clear with a faintyellowish tint. The flocs easily and quickly settled out of thesolutions. In samples treated with active agents at a total of 5 ppm, 10ppm, and 20 ppm, the flocs remained stable for several hours at least;at the higher doses, the flocs were stable overnight. At the lowest dosetested, 2.5 ppm, the fluids also clarified substantially, but the flocswere less stable and began to break apart after about 30 minutes at 95°C.

At somewhat lower temperatures, e.g. 80° C. or less, water clarity wasmore readily achieved and flocs remained stable for longer periods atlower doses, with both the anionic and cationic flocculation formulas(Examples 31 and 33).

Example 38 Separation of Aqueous and Petrochemical Phases of aHigh-Percentage Solids Downstream Process Water from a Waste ReclamationStream

The waste process fluids used in this example were produced from anoil-sands operation after several steps of conventional separation andwater-treatment, resulting in a concentrated residue having a very highlevel (60% or more oily/bituminous materials) of petrochemical materialsemulsified in water. Such waste streams are difficult to clarify evenwith very high doses of conventional treatment chemicals, e.g. 500 to1000 ppm actives, which typically produce incompletely separated aqueousand oily layers.

In this example, use of the formulas of the present invention led torapid and effective separation of the water from the oily/bituminousphases at much lower dosings of chemical additives.

A sample of 400 ml of the oily/bituminous aqueous waste stream describedabove, having approx. 40% water and 60% petrochemical content, waspoured into a flask. To this mixture were added 3.2 ml of 2N HCl, andthe flask was swirled and allowed to equilibrate for 30 seconds to 1minute. A dose of 20 ppm actives of polyEpi/DMA was added, and the flaskagain was swirled and allowed to equilibrate for 30-60 seconds.

To the resulting mixture was added a dose of 40 ppm actives of thecationic PAM/starch flocculant, e.g. as described in Example 33 above,for a total treatment of 60 ppm actives. The flask was swirled to mixand then allowed to sit.

Within a few minutes, a clear aqueous lower phase began to form, with adark oily/bituminous phase on top. Within a few more minutes, the lower,clear, aqueous phase had stabilized at approximately 40% of the totalvolume, with the oily/bituminous phase floating on top.

We claim:
 1. A method of clarifying hydrocarbon- and bitumen-containingprocess water obtained from an oil-sands mining operation, said methodcomprising: adding a coagulant to said process water, wherein saidcoagulant is an aluminum, iron, or calcium salt or a polycationicpolymer; and adding an anionic flocculant to said process water, whereinthe flocculant is an anionic polymer.
 2. The method of claim 1 whereinthe polymeric coagulant is selected from polyaluminate, a polymer ofepichlorohydrin and dimethyl amine (polyEPI/DMA) and/or a polymer ofdiallyl dimethyl ammonium chloride (polyDADMAC).
 3. The method of claim1, wherein said polycationic coagulant is polyEPI/DMA.
 4. The method ofclaim 1 wherein the polymeric coagulant has a molecular weight less than1 million Daltons.
 5. The method of claim 1 wherein the anionicflocculant is an acrylamide/acrylate polymer.
 6. The method of claim 1wherein the anionic flocculant has a molecular weight of at least 1million Daltons and a mole % acrylamide of at least 50%.
 7. The methodof claim 1, wherein said coagulant is added to said process water,together with, or prior to, said anionic acrylamide copolymer
 8. Themethod of claim 1, wherein said process water is acidified prior toadding said coagulant and/or said anionic acrylamide copolymer.
 9. Themethod of claim 8 wherein said process water is acidified to a pH ofabout 2-4.
 10. The method of claim 1, wherein said method comprisesadding a flocculant composition, wherein said composition comprises anactivated, pregelatinized or maleamate-modified starch and said anionicacrylamide copolymer.
 11. The method of claim 10, wherein saidcomposition comprises the activated starch.
 12. The method of claim 11,wherein said composition contains said activated starch and acrylamidecopolymer in a ratio between about 0.1:1 and 100:1.
 13. The method ofclaim 1, wherein the total amount of additives is in the range of about2 ppm to about 500 ppm relative to said process water.
 14. The method ofclaim 13, wherein the total amount of additive is in the range of about2 ppm to about 100 ppm relative to said process water.
 15. The method ofclaim 1, wherein said anionic acrylamide copolymer has a molecularweight of at least 4 million Daltons.
 16. The method of claim 1, whereinsaid polycationic coagulant has a molecular weight less than 500kiloDaltons.
 17. The method of claim 1, comprising the steps of: (a)adjusting the pH of said process water to about 2-4; (b) adding acoagulant to said process water, wherein said coagulant is an inorganicaluminum, iron, or calcium salt, or a polycationic copolymer that has amolecular weight less than 1 million Daltons and a mole % cationicmonomer of at least 50%; and (c) adding a flocculant comprising ananionic acrylamide copolymer and an activated starch to said processwater, wherein said acrylamide copolymer has a molecular weight of atleast 1 million Daltons and a mole % acrylamide of at least 50%.
 18. Themethod of claim 17, wherein the polymeric coagulant is selected from apolymer of polyaluminate, a polymer of epichlorohydrin and dimethylamine (polyEPI/DMA) and/or a polymer of diallyl dimethyl ammoniumchloride (polyDADMAC).
 19. The method of claim 18, wherein saidpolycationic coagulant is polyEPI/DMA.
 20. The method of claim 19,wherein said oil-sand mining operation is steam assisted gravitydrainage (SAGD) operation.